Molecules having pesticidal utility, and intermediates, compositions, and processes, related thereto

ABSTRACT

This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, intermediates used in such processes, pesticidal compositions containing such molecules, and processes of using such pesticidal compositions against such pests. These pesticidal compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides. This document discloses molecules having the following formula (“Formula One”).

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 of U.S.Provisional Patent Application Ser. No. 62/214,325 and 62/214,329, bothfiled Sep. 4, 2015, which are hereby incorporated by reference in theirentireties.

FIELD OF THIS DISCLOSURE

This disclosure relates to the field of molecules having pesticidalutility against pests in Phyla Arthropoda, Mollusca, and Nematoda,processes to produce such molecules, intermediates used in suchprocesses, pesticidal compositions containing such molecules, andprocesses of using such pesticidal compositions against such pests.These pesticidal compositions may be used, for example, as acaricides,insecticides, miticides, molluscicides, and nematicides.

BACKGROUND OF THIS DISCLOSURE

“Many of the most dangerous human diseases are transmitted by insectvectors” (Rivero et al.). “Historically, malaria, dengue, yellow fever,plague, filariasis, louse-borne typhus, trypanomiasis, leishmaniasis,and other vector borne diseases were responsible for more human diseaseand death in the 17^(th) through the early 20^(th) centuries than allother causes combined” (Gubler). Vector-borne diseases are responsiblefor about 17% of the global parasitic and infectious diseases. Malariaalone causes over 800,000 deaths a year, 85% of which occur in childrenunder five years of age. Each year there are about 50 to about 100million cases of dengue fever. A further 250,000 to 500,000 cases ofdengue hemorrhagic fever occur each year (Matthews). Vector controlplays a critical role in the prevention and control of infectiousdiseases. However, insecticide resistance, including resistance tomultiple insecticides, has arisen in all insect species that are majorvectors of human diseases (Rivero et al.). Recently, more than 550arthropod species have developed resistance to at least one pesticide(Whalon et al.). Furthermore, the cases of insect resistance continue toexceed by far the number of cases of herbicide and fungicide resistance(Sparks et al.).

Each year insects, plant pathogens, and weeds, destroy more than 40% ofall food production. This loss occurs despite the application ofpesticides and the use of a wide array of non-chemical controls, suchas, crop rotations, and biological controls. If just some of this foodcould be saved, it could be used to feed the more than three billionpeople in the world who are malnourished (Pimental).

Plant parasitic nematodes are among the most widespread pests, and arefrequently one of the most insidious and costly. It has been estimatedthat losses attributable to nematodes are from about 9% in developedcountries to about 15% in undeveloped countries. However, in the UnitedStates of America a survey of 35 States on various crops indicatednematode-derived losses of up to 25% (Nicol et al.).

It is noted that gastropods (slugs and snails) are pests of lesseconomic importance than other arthropods or nematodes, but in certainplaces, they may reduce yields substantially, severely affecting thequality of harvested products, as well as, transmitting human, animal,and plant diseases. While only a few dozen species of gastropods areserious regional pests, a handful of species are important pests on aworldwide scale. In particular, gastropods affect a wide variety ofagricultural and horticultural crops, such as, arable, pastoral, andfiber crops; vegetables; bush and tree fruits; herbs; and ornamentals(Speiser).

Termites cause damage to all types of private and public structures, aswell as to agricultural and forestry resources. In 2005, it wasestimated that termites cause over US$50 billion in damage worldwideeach year (Korb).

Consequently, for many reasons, including those mentioned above, thereis an on-going need for the costly (estimated to be about US$256 millionper pesticide in 2010), time-consuming (on average about 10 years perpesticide), and difficult, development of new pesticides (CropLifeAmerica).

CERTAIN REFERENCES CITED IN THIS DISCLOSURE

-   CropLife America, The Cost of New Agrochemical Product Discovery,    Development & Registration, and Research & Development predictions    for the Future, 2010.-   Drewes, M., Tietjen, K., Sparks, T. C., High-Throughput Screening in    Agrochemical Research, Modern Methods in Crop Protection Research,    Part I, Methods for the Design and Optimization of New Active    Ingredients, Edited by Jeschke, P., Kramer, W., Schirmer, U., and    Matthias W., p. 1-20, 2012.-   Gubler, D., Resurgent Vector-Borne Diseases as a Global Health    Problem, Emerging Infectious Diseases, Vol. 4, No. 3, p. 442-450,    1998.-   Korb, J., Termites, Current Biology, Vol. 17, No. 23, 2007.-   Matthews, G., Integrated Vector Management: Controlling Vectors of    Malaria and Other Insect Vector Borne Diseases, Ch. 1, p. 1, 2011.-   Nicol, J., Turner S., Coyne, L., den Nijs, L., Hocksland, L.,    Tahna-Maafi, Z., Current Nematode Threats to World Agriculture,    Genomic and Molecular Genetics of Plant—Nematode Interactions, p.    21-43, 2011.-   Pimental, D., Pest Control in World Agriculture, Agricultural    Sciences—Vol. II, 2009.-   Rivero, A., Vezilier, J., Weill, M., Read, A., Gandon, S., Insect    Control of Vector-Borne Diseases: When is Insect Resistance a    Problem? Public Library of Science Pathogens, Vol. 6, No. 8, p. 1-9,    2010.-   Sparks T. C., Nauen R., IRAC: Mode of action classification and    insecticide resistance management, Pesticide Biochemistry and    Physiology (2014) available online 4 Dec. 2014.-   Speiser, B., Molluscicides, Encyclopedia of Pest Management, Ch.    219, p. 506-508, 2002.-   Whalon, M., Mota-Sanchez, D., Hollingworth, R., Analysis of Global    Pesticide Resistance in Arthropods, Global Pesticide Resistance in    Arthropods, Ch. 1, p. 5-33, 2008.

DEFINITIONS USED IN THIS DISCLOSURE

The examples given in these definitions are generally non-exhaustive andmust not be construed as limiting this disclosure. It is understood thata substituent should comply with chemical bonding rules and stericcompatibility constraints in relation to the particular molecule towhich it is attached. These definitions are only to be used for thepurposes of this disclosure.

The phrase “active ingredient” means a material having activity usefulin controlling pests, and/or that is useful in helping other materialshave better activity in controlling pests, examples of such materialsinclude, but are not limited to, acaricides, algicides, antifeedants,avicides, bactericides, bird repellents, chemosterilants, fungicides,herbicide safeners, herbicides, insect attractants, insect repellents,insecticides, mammal repellents, mating disrupters, molluscicides,nematicides, plant activators, plant growth regulators, rodenticides,synergists, and virucides (see alanwood.net). Specific examples of suchmaterials include, but are not limited to, the materials listed inactive ingredient group alpha.

The phrase “active ingredient group alpha” (hereafter “AIGA”) meanscollectively the following materials:

(1) (3-ethoxypropyl)mercury bromide, 1,2-dibromoethane,1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropene, 1-MCP,1-methylcyclopropene, 1-naphthol, 2-(octylthio)ethanol, 2,3,3-TPA,2,3,5-tri-iodobenzoic acid, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, 2,4,5-TP,2,4-D, 2, 4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2,4-MCPA, 2,4-MCPB,2iP, 2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, 3,4-DB,3,4-DP, 3,6-dichloropicolinic acid, 4-aminopyridine, 4-CPA, 4-CPB,4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate,8-phenylmercurioxyquinoline, abamectin, abamectin-aminomethyl, abscisicacid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor,acetofenate, acetophos, acetoprole, acibenzolar, acifluorfen, aclonifen,ACN, acrep, acrinathrin, acrolein, acrylonitrile, acypetacs,afidopyropen, afoxolaner, alachlor, alanap, alanycarb, albendazole,aldicarb, aldicarb sulfone, aldimorph, aldoxycarb, aldrin, allethrin,allicin, allidochlor, allosamidin, alloxydim, allyl alcohol, allyxycarb,alorac, a/pha-cypermethrin, a/pha-endosulfan, alphamethrin, altretamine,aluminium phosphide, aluminum phosphide, ametoctradin, ametridione,ametryn, ametryne, amibuzin, amicarbazone, amicarthiazol, amidithion,amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor,aminopyralid, aminotriazole, amiprofos-methyl, amiprophos,amiprophos-methyl, amisulbrom, amiton, amitraz, amitrole, ammoniumsulfamate, amobam, amorphous silica gel, amorphous silicon dioxide,ampropylfos, AMS, anabasine, ancymidol, anilazine, anilofos, anisuron,anthraquinone, antu, apholate, aramite, arprocarb, arsenous oxide,asomate, aspirin, asulam, athidathion, atraton, atrazine, aureofungin,avermectin B1, AVG, aviglycine, azaconazole, azadirachtin, azafenidin,azamethiphos, azidithion, azimsulfuron, azinphosethyl, azinphos-ethyl,azinphosmethyl, azinphos-methyl, aziprotryn, aziprotryne, azithiram,azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban,barbanate, barium hexafluorosilicate, barium polysulfide, bariumsilicofluoride, barthrin, basic copper carbonate, basic copper chloride,basic copper sulfate, BCPC, beflubutamid, benalaxyl, benalaxyl-M,benazolin, bencarbazone, benclothiaz, bendaqingbingzhi, bendiocarb,bendioxide, benefin, benfluralin, benfuracarb, benfuresate,benmihuangcaoan, benodanil, benomyl, benoxacor, benoxafos, benquinox,bensulfuron, bensulide, bensultap, bentaluron, bentazon, bentazone,benthiavalicarb, benthiazole, benthiocarb, bentranil, benzadox,benzalkonium chloride, benzamacril, benzamizole, benzamorf, benzenehexachloride, benzfendizone, benzimine, benzipram, benzobicyclon,benzoepin, benzofenap, benzofluor, benzohydroxamic acid, benzomate,benzophosphate, benzothiadiazole, benzovindiflupyr, benzoximate,benzoylprop, benzthiazuron, benzuocaotong, benzyl benzoate,benzyladenine, berberine, beta-cyfluthrin, beta-cypermethrin,bethoxazin, BHC, bialaphos, bicyclopyrone, bifenazate, bifenox,bifenthrin, bifujunzhi, bilanafos, binapacryl, bingqingxiao,bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl,bisazir, bismerthiazol, bismerthiazol-copper, bisphenylmercurymethylenedi(x-naphthalene-y-sulphonate), bispyribac, bistrifluron,bisultap, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeauxmixture, boric acid, boscalid, BPPS, brassinolide, brassinolide-ethyl,brevicomin, brodifacoum, brofenprox, brofenvalerate, broflanilide,brofluthrinate, bromacil, bromadiolone, bromchlophos, bromethalin,bromethrin, bromfenvinfos, bromoacetamide, bromobonil, bromobutide,bromociclen, bromocyclen, bromo-DDT, bromofenoxim, bromofos,bromomethane, bromophos, bromophos-ethyl, bromopropylate, bromothalonil,bromoxynil, brompyrazon, bromuconazole, bronopol, BRP, BTH, bucarpolate,bufencarb, buminafos, bupirimate, buprofezin, Burgundy mixture,busulfan, busulphan, butacarb, butachlor, butafenacil, butam, butamifos,butane-fipronil, butathiofos, butenachlor, butene-fipronil, butethrin,buthidazole, buthiobate, buthiuron, butifos, butocarboxim, butonate,butopyronoxyl, butoxycarboxim, butralin, butrizol, butroxydim, buturon,butylamine, butylate, butylchlorophos, butylene-fipronil, cacodylicacid, cadusafos, cafenstrole, calciferol, calcium arsenate, calciumchlorate, calcium cyanamide, calcium cyanide, calcium polysulfide,calvinphos, cambendichlor, camphechlor, camphor, captafol, captan,carbam, carbamorph, carbanolate, carbaril, carbaryl, carbasulam,carbathion, carbendazim, carbendazol, carbetamide, carbofenotion,carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide,carbophenothion, carbophos, carbosulfan, carboxazole, carboxide,carboxin, carfentrazone, carpropamid, cartap, carvacrol, carvone, CAVP,CDAA, CDEA, CDEC, cellocidin, CEPC, ceralure, cerenox, cevadilla,Cheshunt mixture, chinalphos, chinalphos-methyl, chinomethionat,chinomethionate, chiralaxyl, chitosan, chlobenthiazone, chlomethoxyfen,chloralose, chloramben, chloramine phosphorus, chloramphenicol,chloraniformethan, chloranil, chloranocryl, chlorantraniliprole,chlorazifop, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen,chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform,chlorempenthrin, chloretazate, chlorethephon, chlorethoxyfos,chloreturon, chlorfenac, chlorfenapyr, chlorfenazole, chlorfenethol,chlorfenidim, chlorfenprop, chlorfenson, chlorfensulphide,chlorfenvinphos, chlorfenvinphos-methyl, chlorfluazuron, chlorflurazole,chlorflurecol, chlorfluren, chlorflurenol, chloridazon, chlorimuron,chlorinate, chlor-IPC, chlormephos, chlormequat, chlormesulone,chlormethoxynil, chlornidine, chlornitrofen, chloroacetic acid,chlorobenzilate, chlorodinitronaphthalenes, chlorofénizon, chloroform,chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophos,chloropicrin, chloropon, chloroprallethrin, chloropropylate,chlorothalonil, chlorotoluron, chloroxifenidim, chloroxuron,chloroxynil, chlorphonium, chlorphoxim, chlorprazophos, chlorprocarb,chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox,chlorsulfuron, chlorthal, chlorthiamid, chlorthiophos, chlortoluron,chlozolinate, chltosan, cholecalciferol, choline chloride,chromafenozide, cicloheximide, cimectacarb, cimetacarb, cinerin I,cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron,cintofen, ciobutide, cisanilide, cismethrin, clacyfos, clefoxydim,clenpirin, clenpyrin, clethodim, climbazole, cliodinate, clodinafop,cloethocarb, clofencet, clofenotane, clofentezine, clofenvinfos,clofibric acid, clofop, clomazone, clomeprop, clonitralid, cloprop,cloproxydim, clopyralid, cloquintocet, cloransulam, closantel,clothianidin, clotrimazole, cloxyfonac, cloxylacon, clozylacon, CMA,CMMP, CMP, CMU, codlelure, colecalciferol, colophonate, copper8-quinolinolate, copper acetate, copper acetoarsenite, copper arsenate,copper carbonate, basic, copper hydroxide, copper naphthenate, copperoleate, copper oxychloride, copper silicate, copper sulfate, coppersulfate, basic, copper zinc chromate, coumachlor, coumafène, coumafos,coumafuryl, coumaphos, coumatetralyl, coumethoxystrobin, coumithoate,coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, cresylic acid,crimidine, crotamiton, crotoxyfos, crotoxyphos, crufomate, cryolite,cue-lure, cufraneb, cumyleron, cumyluron, cuprobam, cuprous oxide,curcumenol, CVMP, cyanamide, cyanatryn, cyanazine, cyanofenphos,cyanogen, cyanophos, cyanthoate, cyantraniliprole, cyanuric acid,cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclaniliprole,cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin,cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron, cyenopyrafen,cyflufenamid, cyflumetofen, cyfluthrin, cyhalodiamide, cyhalofop,cyhalothrin, cyhexatin, cymiazole, cymoxanil, cyometrinil, cypendazole,cypermethrin, cyperquat, cyphenothrin, cyprazine, cyprazole,cyproconazole, cyprodinil, cyprofuram, cypromid, cyprosulfamide,cyromazine, cythioate, cytrex, daimuron, dalapon, daminozide, dayoutong,dazomet, DBCP, d-camphor, DCB, DCIP, DCPA (Japan), DCPA (USA), DCPTA,DCU, DDD, DDPP, DDT, DDVP, debacarb, decafentin, decamethrin,decarbofuran, deet, dehydroacetic acid, deiquat, delachlor, delnav,deltamethrin, demephion, demephion-O, demephion-S, demeton,demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methyl sulphone, demeton-S-methylsulphon,DEP, depalléthrine, derris, desmedipham, desmetryn, desmetryne,d-fanshiluquebingjuzhi, diafenthiuron, dialifor, dialifos, diallate,di-allate, diamidafos, dianat, diatomaceous earth, diatomite, diazinon,dibrom, dibutyl phthalate, dibutyl succinate, dicamba, dicapthon,dichlobenil, dichlobentiazox, dichlofenthion, dichlofluanid, dichlone,dichloralurea, dichlorbenzuron, dichlorfenidim, dichlorflurecol,dichlorflurenol, dichlormate, dichlormid, dichloromethane, dichlorophen,dichlorprop, dichlorprop-P, dichlorvos, dichlozolin, dichlozoline,diclobutrazol, diclocymet, diclofop, diclomezine, dicloran,dicloromezotiaz, diclosulam, dicofol, dicophane, dicoumarol, dicresyl,dicrotophos, dicryl, dicumarol, dicyclanil, dicyclonon, dieldrin,dienochlor, diethamquat, diethatyl, diethion, diéthion, diethofencarb,dietholate, diéthon, diethyl pyrocarbonate, diethyltoluamide,difenacoum, difenoconazole, difenopenten, difenoxuron, difenzoquat,difethialone, diflovidazin, diflubenzuron, diflufenican, diflufenicanil,diflufenzopyr, diflumetorim, dikegulac, dilor, dimatif, dimefluthrin,dimefox, dimefuron, dimehypo, dimepiperate, dimetachlone, dimetan,dimethacarb, dimethachlone, dimethachlor, dimethametryn, dimethenamid,dimethenamid-P, dimethipin, dimethirimol, dimethoate, dimethomorph,dimethrin, dimethyl carbate, dimethyl disulfide, dimethyl phthalate,dimethylvinphos, dimetilan, dimexano, dimidazon, dimoxystrobin,dimpylate, dimuron, dinex, dingjunezuo, diniconazole, diniconazole-M,dinitramine, dinitrophenols, dinobuton, dinocap, dinocap-4, dinocap-6,dinocton, dinofenate, dinopenton, dinoprop, dinosam, dinoseb,dinosulfon, dinotefuran, dinoterb, dinoterbon, diofenolan,dioxabenzofos, dioxacarb, dioxathion, dioxation, diphacin, diphacinone,diphenadione, diphenamid, diphenamide, diphenyl sulfone, diphenylamine,diphenylsulphide, diprogulic acid, dipropalin, dipropetryn, dipterex,dipymetitrone, dipyrithione, diquat, disodium tetraborate, disosultap,disparlure, disugran, disul, disulfiram, disulfoton, ditalimfos,dithianon, dithicrofos, dithioether, dithiométon, dithiopyr, diuron,dixanthogen, d-limonene, DMDS, DMPA, DNOC, dodemorph, dodicin, dodine,dofenapyn, doguadine, dominicalure, doramectin, DPC, drazoxolon, DSMA,d-trans-allethrin, d-trans-resmethrin, dufulin, dymron, EBEP, EBP,ebufos, ecdysterone, echlomezol, EDB, EDC, EDDP, edifenphos, eglinazine,emamectin, EMPC, empenthrin, enadenine, endosulfan, endothal, endothall,endothion, endrin, enestroburin, enilconazole, enoxastrobin,ephirsulfonate, EPN, epocholeone, epofenonane, epoxiconazole,eprinomectin, epronaz, epsilon-metofluthrin, epsilon-momfluorothrin,EPTC, erbon, ergocalciferol, erlujixiancaoan, esdépalléthrine,esfenvalerate, ESP, esprocarb, etacelasil, etaconazole, etaphos, etem,ethaboxam, ethachlor, ethalfluralin, ethametsulfuron, ethaprochlor,ethephon, ethidimuron, ethiofencarb, ethiolate, ethion, ethiozin,ethiprole, ethirimol, ethoate-methyl, ethobenzanid, ethofumesate,ethohexadiol, ethoprop, ethoprophos, ethoxyfen, ethoxyquin,ethoxysulfuron, ethychlozate, ethyl formate, ethyl pyrophosphate,ethylan, ethyl-DDD, ethylene, ethylene dibromide, ethylene dichloride,ethylene oxide, ethylicin, ethylmercury 2,3-dihydroxypropyl mercaptide,ethylmercury acetate, ethylmercury bromide, ethylmercury chloride,ethylmercury phosphate, etinofen, ETM, etnipromid, etobenzanid,etofenprox, etoxazole, etridiazole, etrimfos, étrimphos, eugenol, EXD,famoxadone, famphur, fenac, fenamidone, fenaminosulf, fenaminstrobin,fenamiphos, fenapanil, fenarimol, fenasulam, fenazaflor, fenazaquin,fenbuconazole, fenbutatin oxide, fenchlorazole, fenchlorphos, fenclofos,fenclorim, fenethacarb, fenfluthrin, fenfuram, fenhexamid, fenidin,fenitropan, fenitrothion, fénizon, fenjuntong, fenobucarb, fenolovo,fenoprop, fenothiocarb, fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-P,fenoxasulfone, fenoxycarb, fenpiclonil, fenpirithrin, fenpropathrin,fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate,fenquinotrione, fenridazon, fenson, fensulfothion, fenteracol,fenthiaprop, fenthion, fenthion-ethyl, fentiaprop, fentin, fentrazamide,fentrifanil, fenuron, fenuron-TCA, fenvalerate, ferbam, ferimzone,ferric phosphate, ferrous sulfate, fipronil, flamprop, flamprop-M,flazasulfuron, flocoumafen, flometoquin, flonicamid, florasulam,florpyrauxifen, fluacrypyrim, fluazaindolizine, fluazifop, fluazifop-P,fluazinam, fluazolate, fluazuron, flubendiamide, flubenzimine,flubrocythrinate, flucarbazone, flucetosulfuron, fluchloralin,flucofuron, flucycloxuron, flucythrinate, fludioxonil, fluénéthyl,fluenetil, fluensulfone, flufenacet, flufenerim, flufenican,flufenoxuron, flufenoxystrobin, flufenprox, flufenpyr, flufenzine,flufiprole, fluhexafon, flumethrin, flumetover, flumetralin,flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, flumorph,fluometuron, fluopicolide, fluopyram, fluorbenside, fluoridamid,fluoroacetamide, fluoroacetic acid, fluorochloridone, fluorodifen,fluoroglycofen, fluoroimide, fluoromide, fluoromidine, fluoronitrofen,fluoroxypyr, fluothiuron, fluotrimazole, fluoxastrobin, flupoxam,flupropacil, flupropadine, flupropanate, flupyradifurone,flupyrsulfuron, fluquinconazole, fluralaner, flurazole, flurecol,flurenol, fluridone, flurochloridone, fluromidine, fluroxypyr,flurprimidol, flursulamid, flurtamone, flusilazole, flusulfamide,flutenzine, fluthiacet, fluthiamide, flutianil, flutolanil, flutriafol,fluvalinate, fluxametamide, fluxapyroxad, fluxofenim, folpel, folpet,fomesafen, fonofos, foramsulfuron, forchlorfenuron, formaldehyde,formetanate, formothion, formparanate, fosamine, fosetyl, fosmethilan,fospirate, fosthiazate, fosthietan, frontalin, fthalide, fuberidazole,fucaojing, fucaomi, fujunmanzhi, fulumi, fumarin, funaihecaoling,fuphenthiourea, furalane, furalaxyl, furamethrin, furametpyr, furantebufenozide, furathiocarb, furcarbanil, furconazole, furconazole-cis,furethrin, furfural, furilazole, furmecyclox, furophanate, furyloxyfen,gamma-BHC, gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid,gibberellin A3, gibberellins, gliftor, glitor, glucochloralose,glufosinate, glufosinate-P, glyodin, glyoxime, glyphosate, glyphosine,gossyplure, grandlure, griseofulvin, guanoctine, guazatine, halacrinate,halauxifen, halfenprox, halofenozide, halosafen, halosulfuron,haloxydine, haloxyfop, haloxyfop-P, haloxyfop-R, HCA, HCB, HCH, hemel,hempa, HEOD, heptachlor, heptafluthrin, heptenophos, heptopargil,herbimycin, herbimycin A, heterophos, hexachlor, hexachloran,hexachloroacetone, hexachlorobenzene, hexachlorobutadiene,hexachlorophene, hexaconazole, hexaflumuron, hexafluoramin, hexaflurate,hexalure, hexamide, hexazinone, hexylthiofos, hexythiazox, HHDN,holosulf, homobrassinolide, huancaiwo, huanchongjing, huangcaoling,huanjunzuo, hydramethylnon, hydrargaphen, hydrated lime, hydrogencyanamide, hydrogen cyanide, hydroprene, hydroxyisoxazole, hymexazol,hyquincarb, IAA, IBA, IBP, icaridin, imazalil, imazamethabenz, imazamox,imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron,imibenconazole, imicyafos, imidacloprid, imidaclothiz, iminoctadine,imiprothrin, inabenfide, indanofan, indaziflam, indoxacarb, inezin,infusorial earth, iodobonil, iodocarb, iodofenphos, iodomethane,iodosulfuron, iofensulfuron, ioxynil, ipazine, IPC, ipconazole,ipfencarbazone, ipfentrifluconazole, iprobenfos, iprodione,iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, IPX, isamidofos,isazofos, isobenzan, isocarbamid, isocarbamide, isocarbophos, isocil,isodrin, isofenphos, isofenphos-methyl, isofetamid, isolan,isomethiozin, isonoruron, isopamphos, isopolinate, isoprocarb,isoprocil, isopropalin, isopropazol, isoprothiolane, isoproturon,isopyrazam, isopyrimol, isothioate, isotianil, isouron, isovaledione,isoxaben, isoxachlortole, isoxadifen, isoxaflutole, isoxapyrifop,isoxathion, isuron, ivermectin, ixoxaben, izopamfos, izopamphos,japonilure, japothrins, jasmolin I, jasmolin II, jasmonic acid,jiahuangchongzong, jiajizengxiaolin, jiaxiangjunzhi, jiecaowan,jiecaoxi, Jinganmycin A, jodfenphos, juvenile hormone I, juvenilehormone II, juvenile hormone III, kadethrin, kappa-bifenthrin,kappa-tefluthrin, karbutilate, karetazan, kasugamycin, kejunlin,kelevan, ketospiradox, kieselguhr, kinetin, kinoprene, kiralaxyl,kresoxim-methyl, kuicaoxi, lactofen, lambda-cyhalothrin, lancotrione,latilure, lead arsenate, lenacil, lepimectin, leptophos, lianbenjingzhi,lime sulfur, lindane, lineatin, linuron, lirimfos, litlure, looplure,lufenuron, lufuqingchongxianan, lüxiancaolin, lvdingjunzhi, lvfumijvzhi,lvxiancaolin, lythidathion, M-74, M-81, MAA, magnesium phosphide,malathion, maldison, maleic hydrazide, malonoben, maltodextrin, MAMA,mancopper, mancozeb, mandestrobin, mandipropamid, maneb, matrine,mazidox, MCC, MCP, MCPA, MCPA-thioethyl, MCPB, MCPP, mebenil, mecarbam,mecarbinzid, mecarphon, mecoprop, mecoprop-P, medimeform, medinoterb,medlure, mefenacet, mefenoxam, mefenpyr, mefentrifluconazole,mefluidide, megatomoic acid, melissyl alcohol, melitoxin, MEMC, menazon,MEP, mepanipyrim, meperfluthrin, mephenate, mephosfolan, mepiquat,mepronil, meptyldinocap, mercaptodimethur, mercaptophos, mercaptophosthiol, mercaptothion, mercuric chloride, mercuric oxide, mercurouschloride, merphos, merphos oxide, mesoprazine, mesosulfuron, mesotrione,mesulfen, mesulfenfos, mesulphen, metacresol, metaflumizone, metalaxyl,metalaxyl-M, metaldehyde, metam, metamifop, metamitron, metaphos,metaxon, metazachlor, metazosulfuron, metazoxolon, metconazole, metepa,metflurazon, methabenzthiazuron, methacrifos, methalpropalin, metham,methamidophos, methasulfocarb, methazole, methfuroxam, methibenzuron,methidathion, methiobencarb, methiocarb, methiopyrisulfuron, methiotepa,methiozolin, methiuron, methocrotophos, métholcarb, methometon,methomyl, methoprene, methoprotryn, methoprotryne, methoquin-butyl,methothrin, methoxychlor, methoxyfenozide, methoxyphenone, methylapholate, methyl bromide, methyl eugenol, methyl iodide, methylisothiocyanate, methyl parathion, methylacetophos, methylchloroform,methyldithiocarbamic acid, methyldymron, methylene chloride,methyl-isofenphos, methylmercaptophos, methylmercaptophos oxide,methylmercaptophos thiol, methylmercury benzoate, methylmercurydicyandiamide, methylmercury pentachlorophenoxide, methylneodecanamide,methylnitrophos, methyltriazothion, metiozolin, metiram, metiram-zinc,metobenzuron, metobromuron, metofluthrin, metolachlor, metolcarb,metometuron, metominostrobin, metosulam, metoxadiazone, metoxuron,metrafenone, metriam, metribuzin, metrifonate, metriphonate,metsulfovax, metsulfuron, mevinphos, mexacarbate, miechuwei, mieshuan,miewenjuzhi, milbemectin, milbemycin oxime, milneb, mimanan, mipafox,MIPC, mirex, MNAF, moguchun, molinate, molosultap, momfluorothrin,monalide, monisuron, monoamitraz, monochloroacetic acid, monocrotophos,monolinuron, monomehypo, monosulfiram, monosulfuron, monosultap,monuron, monuron-TCA, morfamquat, moroxydine, morphothion, morzid,moxidectin, MPMC, MSMA, MTMC, muscalure, myclobutanil, myclozolin,myricyl alcohol, N-(ethylmercury)-p-toluenesulphonanilide, NAA, NAAm,nabam, naftalofos, naled, naphthalene, naphthaleneacetamide, naphthalicanhydride, naphthalophos, naphthoxyacetic acids, naphthylacetic acids,naphthylindane-1,3-diones, naphthyloxyacetic acids, naproanilide,napropamide, napropamide-M, naptalam, natamycin, NBPOS, neburea,neburon, nendrin, neonicotine, nichlorfos, niclofen, niclosamide,nicobifen, nicosulfuron, nicotine, nicotine sulfate, nifluridide,nikkomycins, NIP, nipyraclofen, nipyralofen, nitenpyram, nithiazine,nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen,nitrostyrene, nitrothal-isopropyl, nobormide, nonanol, norbormide,norea, norflurazon, nornicotine, noruron, novaluron, noviflumuron, NPA,nuarimol, nuranone, OCH, octachlorodipropyl ether, octhilinone,o-dichlorobenzene, ofurace, omethoate, o-phenylphenol, orbencarb,orfralure, orthobencarb, ortho-dichlorobenzene, orthosulfamuron,oryctalure, orysastrobin, oryzalin, osthol, osthole, ostramone, ovatron,ovex, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl,oxapyrazon, oxapyrazone, oxasulfuron, oxathiapiprolin, oxaziclomefone,oxine-copper, oxine-Cu, oxolinic acid, oxpoconazole, oxycarboxin,oxydemeton-methyl, oxydeprofos, oxydisulfoton, oxyenadenine,oxyfluorfen, oxymatrine, oxytetracycline, oxythioquinox, PAC,paclobutrazol, paichongding, palléthrine, PAP, para-dichlorobenzene,parafluron, paraquat, parathion, parathion-methyl, parinol, Paris green,PCNB, PCP, PCP-Na, p-dichlorobenzene, PDJ, pebulate, pédinex,pefurazoate, pelargonic acid, penconazole, pencycuron, pendimethalin,penfenate, penflufen, penfluron, penoxalin, penoxsulam,pentachlorophenol, pentachlorophenyl laurate, pentanochlor,penthiopyrad, pentmethrin, pentoxazone, perchlordecone, perfluidone,permethrin, pethoxamid, PHC, phenamacril, phenamacril-ethyl,phénaminosulf, phenazine oxide, phénétacarbe, phenisopham, phenkapton,phenmedipham, phenmedipham-ethyl, phenobenzuron, phenothiol, phenothrin,phenproxide, phenthoate, phenylmercuriurea, phenylmercury acetate,phenylmercury chloride, phenylmercury derivative of pyrocatechol,phenylmercury nitrate, phenylmercury salicylate, phorate, phosacetim,phosalone, phosametine, phosazetim, phosazetin, phoscyclotin,phosdiphen, phosethyl, phosfolan, phosfolan-methyl, phosglycin, phosmet,phosnichlor, phosphamide, phosphamidon, phosphine, phosphinothricin,phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide,phthalophos, phthalthrin, picarbutrazox, picaridin, picloram,picolinafen, picoxystrobin, pimaricin, pindone, pinoxaden, piperalin,piperazine, piperonyl butoxide, piperonyl cyclonene, piperophos,piproctanly, piproctanyl, piprotal, pirimetaphos, pirimicarb, piriminil,pirimioxyphos, pirimiphos-ethyl, pirimiphos-methyl, pival, pivaldione,plifenate, PMA, PMP, polybutenes, polycarbamate, polychlorcamphene,polyethoxyquinoline, polyoxin D, polyoxins, polyoxorim, polythialan,potassium arsenite, potassium azide, potassium cyanate, potassiumethylxanthate, potassium naphthenate, potassium polysulfide, potassiumthiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precoceneIII, pretilachlor, primidophos, primisulfuron, probenazole, prochloraz,proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol,profluralin, profluthrin, profoxydim, profurite-aminium, proglinazine,prohexadione, prohydrojasmon, promacyl, promecarb, prometon, prometryn,prometryne, promurit, pronamide, propachlor, propafos, propamidine,propamocarb, propanil, propaphos, propaquizafop, propargite,proparthrin, propazine, propetamphos, propham, propiconazole, propidine,propineb, propisochlor, propoxur, propoxycarbazone, propyl isome,propyrisulfuron, propyzamide, proquinazid, prosuler, prosulfalin,prosulfocarb, prosulfuron, prothidathion, prothiocarb, prothioconazole,prothiofos, prothoate, protrifenbute, proxan, prymidophos, prynachlor,psoralen, psoralene, pydanon, pydiflumetofen, pyflubumide, pymetrozine,pyracarbolid, pyraclofos, pyraclonil, pyraclostrobin, pyraflufen,pyrafluprole, pyramat, pyrametostrobin, pyraoxystrobin, pyrasulfotole,pyraziflumid, pyrazolate, pyrazolynate, pyrazon, pyrazophos,pyrazosulfuron, pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl,pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben, pyridafol,pyridalyl, pyridaphenthion, pyridaphenthione, pyridate, pyridinitril,pyrifenox, pyrifluquinazon, pyriftalid, pyrimetaphos, pyrimethanil,pyrimicarbe, pyrimidifen, pyriminobac, pyriminostrobin,pyrimiphos-ethyl, pyrimiphos-methyl, pyrimisulfan, pyrimitate,pyrinuron, pyriofenone, pyriprole, pyripropanol, pyriproxyfen,pyrisoxazole, pyrithiobac, pyrolan, pyroquilon, pyroxasulfone,pyroxsulam, pyroxychlor, pyroxyfur, qincaosuan, qingkuling, quassia,quinacetol, quinalphos, quinalphos-methyl, quinazamid, quinclorac,quinconazole, quinmerac, quinoclamine, quinofumelin, quinomethionate,quinonamid, quinothion, quinoxyfen, quintiofos, quintozene, quizalofop,quizalofop-P, quwenzhi, quyingding, rabenzazole, rafoxanide,R-diniconazole, rebemide, reglone, renriduron, rescalure, resmethrin,rhodethanil, rhodojaponin-III, ribavirin, rimsulfuron, rizazole,R-metalaxyl, rodéthanil, ronnel, rotenone, ryania, sabadilla,saflufenacil, saijunmao, saisentong, salicylanilide, salifluofen,sanguinarine, santonin, S-bioallethrin, schradan, scilliroside,sebuthylazine, secbumeton, sedaxane, selamectin, semiamitraz, sesamex,sesamolin, sesone, sethoxydim, sevin, shuangjiaancaolin,shuangjianancaolin, S-hydroprene, siduron, sifumijvzhi, siglure,silafluofen, silatrane, silica aerogel, silica gel, silthiofam,silthiopham, silthiophan, silvex, simazine, simeconazole, simeton,simetryn, simetryne, sintofen, S-kinoprene, slaked lime, SMA,S-methoprene, S-metolachlor, sodium arsenite, sodium azide, sodiumchlorate, sodium cyanide, sodium fluoride, sodium fluoroacetate, sodiumhexafluorosilicate, sodium naphthenate, sodium o-phenylphenoxide, sodiumorthophenylphenoxide, sodium pentachlorophenate, sodiumpentachlorophenoxide, sodium polysulfide, sodium silicofluoride, sodiumtetrathiocarbonate, sodium thiocyanate, solan, sophamide, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, spiroxamine,stirofos, streptomycin, strychnine, sulcatol, sulcofuron, sulcotrione,sulfallate, sulfentrazone, sulfiram, sulfluramid, sulfodiazole,sulfometuron, sulfosate, sulfosulfuron, sulfotep, sulfotepp,sulfoxaflor, sulfoxide, sulfoxime, sulfur, sulfuric acid, sulfurylfluoride, sulglycapin, sulphosate, sulprofos, sultropen, swep,tau-fluvalinate, tavron, tazimcarb, TBTO, TBZ, TCA, TCBA, TCMTB, TCNB,TDE, tebuconazole, tebufenozide, tebufenpyrad, tebufloquin,tebupirimfos, tebutam, tebuthiuron, tecloftalam, tecnazene, tecoram,tedion, teflubenzuron, tefluthrin, tefuryltrione, tembotrione, temefos,temephos, tepa, TEPP, tepraloxydim, teproloxydim, terallethrin,terbacil, terbucarb, terbuchlor, terbufos, terbumeton, terbuthylazine,terbutol, terbutryn, terbutryne, terraclor, terramicin, terramycin,tetcyclacis, tetrachloroethane, tetrachlorvinphos, tetraconazole,tetradifon, tetradisul, tetrafluron, tetramethrin, tetra methylfluthrin,tetramine, tetranactin, tetraniliprole, tetrapion, tetrasul, thalliumsulfate, thallous sulfate, thenylchlor, theta-cypermethrin,thiabendazole, thiacloprid, thiadiazine, thiadifluor, thiamethoxam,thiameturon, thiapronil, thiazafluron, thiazfluron, thiazone, thiazopyr,thicrofos, thicyofen, thidiazimin, thidiazuron, thiencarbazone,thifensulfuron, thifluzamide, thimerosal, thimet, thiobencarb,thiocarboxime, thiochlorfenphim, thiochlorphenphime,thiocyanatodinitrobenzenes, thiocyclam, thiodan, thiodiazole-copper,thiodicarb, thiofanocarb, thiofanox, thiofluoximate, thiohempa,thiomersal, thiometon, thionazin, thiophanate, thiophanate-ethyl,thiophanate-methyl, thiophos, thioquinox, thiosemicarbazide, thiosultap,thiotepa, thioxamyl, thiram, thiuram, thuringiensin, tiabendazole,tiadinil, tiafenacil, tiaojiean, TIBA, tifatol, tiocarbazil, tioclorim,tioxazafen, tioxymid, tirpate, TMTD, tolclofos-methyl, tolfenpyrad,tolprocarb, tolpyralate, tolyfluanid, tolylfluanid, tolylmercuryacetate, tomarin, topramezone, toxaphene, TPN, tralkoxydim,tralocythrin, tralomethrin, tralopyril, transfluthrin, transpermethrin,tretamine, triacontanol, triadimefon, triadimenol, triafamone,triallate, tri-allate, triamiphos, triapenthenol, triarathene,triarimol, triasulfuron, triazamate, triazbutil, triaziflam, triazophos,triazothion, triazoxide, tribasic copper chloride, tribasic coppersulfate, tribenuron, tribufos, tributyltin oxide, tricamba, trichlamide,trichlopyr, trichlorfon, trichlormetaphos-3, trichloronat,trichloronate, trichlorotrinitrobenzenes, trichlorphon, triclopyr,triclopyricarb, tricresol, tricyclazole, tricyclohexyltin hydroxide,tridemorph, tridiphane, trietazine, trifenmorph, trifenofos,trifloxystrobin, trifloxysulfuron, trifludimoxazin, triflumezopyrim,triflumizole, triflumuron, trifluralin, triflusulfuron, trifop,trifopsime, triforine, trihydroxytriazine, trimedlure, trimethacarb,trimeturon, trinexapac, triphenyltin, triprene, tripropindan,triptolide, tritac, trithialan, triticonazole, tritosulfuron,trunc-call, tuoyelin, uniconazole, uniconazole-P, urbacide, uredepa,valerate, validamycin, validamycin A, valifenalate, valone, vamidothion,vangard, vaniliprole, vernolate, vinclozolin, vitamin D3, warfarin,xiaochongliulin, xinjunan, xiwojunan, xiwojunzhi, XMC, xylachlor,xylenols, xylylcarb, xymiazole, yishijing, zarilamid, zeatin,zengxiaoan, zengxiaolin, zeta-cypermethrin, zinc naphthenate, zincphosphide, zinc thiazole, zinc thiozole, zinc trichlorophenate, zinctrichlorophenoxide, zineb, ziram, zolaprofos, zoocoumarin, zoxamide,zuoanjunzhi, zuocaoan, zuojunzhi, zuomihuanglong, α-chlorohydrin,α-ecdysone, α-multistriatin, α-naphthaleneacetic acids, and 3-ecdysone;

(2) the following molecules

-   -   (a)        N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide        (hereafter “AI-1”)

-   -   (b)        (3S,6S,7R,8R)-8-benzyl-3-(3-((isobutyryloxy)methoxy)-4-methoxypicolinamido)-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl        isobutyrate (hereafter “AI-2”)

(3) a molecule known as Lotilaner that has the following structure

and

(4) the following molecules in Table A

TABLE A Structure of M#-active ingredients M# Structure M1

M2

M3

M4

M5

M6

As used in this disclosure, each of the above is an active ingredient.For more information consult the “Compendium of Pesticide Common Names”located at Alanwood.net and various editions, including the on-lineedition, of “The Pesticide Manual” located at bcpcdata.com.

A particularly preferred selection of active ingredients are1,3-dichloropropene, chlorpyrifos, hexaflumuron, methoxyfenozide,noviflumuron, spinetoram, spinosad, sulfoxaflor, and sulfuryl fluoride(hereafter “AIGA-2”).

Additionally, another particularly preferred selection of activeingredients are acequinocyl, acetamiprid, acetoprole, avermectin,azinphos-methyl, bifenazate, bifenthrin, carbaryl, carbofuran,chlorfenapyr, chlorfluazuron, chromafenozide, clothianidin, cyfluthrin,cypermethrin, deltamethrin, diafenthiuron, emamectin benzoate,endosulfan, esfenvalerate, ethiprole, etoxazole, fipronil, flonicamid,fluacrypyrim, gamma-cyhalothrin, halofenozide, indoxacarb,lambda-cyhalothrin, lufenuron, malathion, methomyl, novaluron,permethrin, pyridalyl, pyrimidifen, spirodiclofen, tebufenozide,thiacloprid, thiamethoxam, thiodicarb, tolfenpyrad, andzeta-cypermethrin (hereafter “AIGA-3”).

The term “alkenyl” means an acyclic, unsaturated (at least onecarbon-carbon double bond), branched or unbranched, substituentconsisting of carbon and hydrogen, for example, vinyl, allyl, butenyl,pentenyl, and hexenyl.

The term “alkenyloxy” means an alkenyl further consisting of acarbon-oxygen single bond, for example, allyloxy, butenyloxy,pentenyloxy, hexenyloxy.

The term “alkoxy” means an alkyl further consisting of a carbon-oxygensingle bond, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, and tert-butoxy.

The term “alkyl” means an acyclic, saturated, branched or unbranched,substituent consisting of carbon and hydrogen, for example, methyl,ethyl, propyl, isopropyl, butyl, and tert-butyl.

The term “alkynyl” means an acyclic, unsaturated (at least onecarbon-carbon triple bond), branched or unbranched, substituentconsisting of carbon and hydrogen, for example, ethynyl, propargyl,butynyl, and pentynyl.

The term “alkynyloxy” means an alkynyl further consisting of acarbon-oxygen single bond, for example, pentynyloxy, hexynyloxy,heptynyloxy, and octynyloxy.

The term “aryl” means a cyclic, aromatic substituent consisting ofhydrogen and carbon, for example, phenyl, naphthyl, and biphenyl.

The term “biopesticide” means a microbial biological pest control agentthat, in general, is applied in a similar manner to chemical pesticides.Commonly they are bacterial, but there are also examples of fungalcontrol agents, including Trichoderma spp. and Ampelomyces quisqualis.One well-known biopesticide example is Bacillus species, a bacterialdisease of Lepidoptera, Coleoptera, and Diptera. Biopesticides includeproducts based on entomopathogenic fungi (e.g. Metarhizium anisopliae),entomopathogenic nematodes (e.g. Steinernema feltiae), andentomopathogenic viruses (e.g. Cydia pomonella granulovirus). Otherexamples of entomopathogenic organisms include, but are not limited to,baculoviruses, protozoa, and Microsporidia. For the avoidance of doubt,biopesticides are active ingredients.

The term “cycloalkenyl” means a monocyclic or polycyclic, unsaturated(at least one carbon-carbon double bond) substituent consisting ofcarbon and hydrogen, for example, cyclobutenyl, cyclopentenyl,cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl, tetrahydronaphthyl,hexahydronaphthyl, and octahydronaphthyl.

The term “cycloalkenyloxy” means a cycloalkenyl further consisting of acarbon-oxygen single bond, for example, cyclobutenyloxy,cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.

The term “cycloalkyl” means a monocyclic or polycyclic, saturatedsubstituent consisting of carbon and hydrogen, for example, cyclopropyl,cyclobutyl, cyclopentyl, norbornyl, bicyclo[2.2.2]octyl, anddecahydronaphthyl.

The term “cycloalkoxy” means a cycloalkyl further consisting of acarbon-oxygen single bond, for example, cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, norbornyloxy, and bicyclo[2.2.2]octyloxy.

The term “halo” means fluoro, chloro, bromo, and iodo.

The term “haloalkoxy” means an alkoxy further consisting of, from one tothe maximum possible number of identical or different, halos, forexample, fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy,chloromethoxy, trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, andpentafluoroethoxy.

The term “haloalkyl” means an alkyl further consisting of, from one tothe maximum possible number of, identical or different, halos, forexample, fluoromethyl, trifluoromethyl, 2,2-difluoropropyl,chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.

The term “heterocyclyl” means a cyclic substituent that may be aromatic,fully saturated, or partially or fully unsaturated, where the cyclicstructure contains at least one carbon and at least one heteroatom,where said heteroatom is nitrogen, sulfur, or oxygen. Examples are:

(1) aromatic heterocyclyl substituents include, but are not limited to,benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzothienyl,benzothiazolyl, benzoxazolyl, cinnolinyl, furanyl, imidazolyl,indazolyl, indolyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl,oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl,pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl,quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl,triazinyl, and triazolyl;

(2) fully saturated heterocyclyl substituents include, but are notlimited to, piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl,tetrahydrofuranyl, and tetrahydropyranyl;

(3) partially or fully unsaturated heterocyclyl substituents include,but are not limited to, 4,5-dihydro-isoxazolyl, 4,5-dihydro-oxazolyl,4,5-dihydro-1H-pyrazolyl, 2,3-dihydro-[1,3,4]-oxadiazolyl, and1,2,3,4-tetrahydro-quinolinyl; and

(4) Additional examples of heterocyclyls include the following:

-   -   thietanyl thietanyl-oxide and thietanyl-dioxide.

The term “locus” means a habitat, breeding ground, plant, seed, soil,material, or environment, in which a pest is growing, may grow, or maytraverse. For example, a locus may be: where crops, trees, fruits,cereals, fodder species, vines, turf, and/or ornamental plants, aregrowing; where domesticated animals are residing; the interior orexterior surfaces of buildings (such as places where grains are stored);the materials of construction used in buildings (such as impregnatedwood); and the soil around buildings.

The phrase “MoA Material” means an active ingredient having a mode ofaction (“MoA”) as indicated in IRAC MoA Classification v. 7.4, locatedat irac-online.org., which describes the following groups.

(1) Acetylcholinesterase (AChE) inhibitors, includes the followingactive ingredients acephate, alanycarb, aldicarb, azamethiphos,azinphos-ethyl, azinphos-methyl, bendiocarb, benfuracarb, butocarboxim,butoxycarboxim, cadusafos, carbaryl, carbofuran, carbosulfan,chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos,chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon,dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton,EPN, ethiofencarb, ethion, ethoprophos, famphur, fenamiphos,fenitrothion, fenobucarb, fenthion, formetanate, fosthiazate,furathiocarb, heptenophos, imicyafos, isofenphos, isoprocarb, isopropylO-(methoxyaminothio-phosphoryl)salicylate, isoxathion, malathion,mecarbam, methamidophos, methidathion, methiocarb, methomyl, metolcarb,mevinphos, monocrotophos, Naled, omethoate, oxamyl, oxydemeton-methyl,parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet,phosphamidon, phoxim, pirimicarb, pirimiphos-methyl, profenofos,propetamphos, propoxur, prothiofos, pyraclofos, pyridaphenthion,quinalphos, sulfotep, tebupirimfos, temephos, terbufos,tetrachlorvinphos, thiodicarb, thiofanox, thiometon, triazamate,triazophos, trichlorfon, trimethacarb, vamidothion, XMC, and xylylcarb.

(2) GABA-gated chloride channel antagonists, includes the followingactive ingredients chlordane, endosulfan, ethiprole, and fipronil.

(3) Sodium channel modulators, includes the following active ingredientsacrinathrin, allethrin, d-cis-trans-allethrin, d-trans-allethrin,bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin,cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin,beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin[(1R)-trans-isomers], deltamethrin, empenthrin [(EZ)-(1R)-isomers],esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate,flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin,permethrin, phenothrin [(1R)-trans-isomer], prallethrin, pyrethrins(pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin,tetramethrin [(1R)-isomers], tralomethrin, and transfluthrin, andmethoxychlor.

(4) Nicotinic acetylcholine receptor (nAChR) agonists, includes thefollowing active ingredients

-   -   (4A) acetamiprid, clothianidin, dinotefuran, imidacloprid,        nitenpyram, thiacloprid, thiamethoxam,    -   (4B) nicotine,    -   (4C) sulfoxaflor,    -   (4D) flupyradifurone,    -   (4E) triflumezopyrim and dicloromezotiaz.

(5) Nicotinic acetylcholine receptor (nAChR) allosteric activators,includes the following active ingredients spinetoram and spinosad.

(6) Chloride channel activators, includes the following activeingredients abamectin, emamectin benzoate, lepimectin, and milbemectin.

(7) Juvenile hormone mimics, includes the following active ingredientshydroprene, kinoprene, methoprene, fenoxycarb, and pyriproxyfen.

(8) Miscellaneous nonspecific (multi-site) inhibitors, includes thefollowing active ingredients methyl bromide, chloropicrin, sulfurylfluoride, borax, boric acid, disodium octaborate, sodium borate, sodiummetaborate, tartar emetic, diazomet, and metam.

(9) Modulators of Chordotonal Organs, includes the following activeingredients pymetrozine and flonicamid.

(10) Mite growth inhibitors, includes the following active ingredientsclofentezine, hexythiazox, diflovidazin, and etoxazole.

(11) Microbial disruptors of insect midgut membranes, includes thefollowing active ingredients Bacillus thuringiensis subsp. israelensis,Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp.kurstaki, Bacillus thuringiensis subsp. tenebrionenis, Bt crop proteins(Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab,Cry3Bb, Cry34Ab1/Cry35Ab1), and Bacillus sphaericus.

(12) Inhibitors of mitochondrial ATP synthase, includes the followingactive ingredients tetradifon, propargite, azocyclotin, cyhexatin,fenbutatin oxide, and diafenthiuron.

(13) Uncouplers of oxidative phosphorylation via disruption of theproton gradient, includes the following active ingredients chlorfenapyr,DNOC, and sulfluramid.

(14) Nicotinic acetylcholine receptor (nAChR) channel blockers, includesthe following active ingredients bensultap, cartap hydrochloride,thiocyclam, and thiosultap-sodium.

(15) Inhibitors of chitin biosynthesis, type 0, includes the followingactive ingredients bistrifluron, chlorfluazuron, diflubenzuron,flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron, teflubenzuron, and triflumuron.

(16) Inhibitors of chitin biosynthesis, type 1, includes the followingactive ingredient buprofezin.

(17) Moulting disruptor, Dipteran, includes the following activeingredient cyromazine.

(18) Ecdysone receptor agonists, includes the following activeingredients chromafenozide, halofenozide, methoxyfenozide, andtebufenozide.

(19) Octopamine receptor agonists, includes the following activeingredient amitraz.

(20) Mitochondrial complex III electron transport inhibitors, includesthe following active ingredients hydramethylnon, acequinocyl, andfluacrypyrim.

(21) Mitochondrial complex I electron transport inhibitors, includes thefollowing active ingredients fenazaquin, fenpyroximate, pyrimidifen,pyridaben, tebufenpyrad, tolfenpyrad, and rotenone.

(22) Voltage-dependent sodium channel blockers, includes the followingactive ingredients indoxacarb and metaflumizone.

(23) Inhibitors of acetyl CoA carboxylase, includes the following activeingredients spirodiclofen, spiromesifen, and spirotetramat.

(24) Mitochondrial complex IV electron transport inhibitors, includesthe following active ingredients, aluminium phosphide, calciumphosphide, phosphine, zinc phosphide, and cyanide.

(25) Mitochondrial complex II electron transport inhibitors, includesthe following active ingredients cyenopyrafen, cyflumetofen, andpyflubumide, and (28) Ryanodine receptor modulators, includes thefollowing active ingredients chlorantraniliprole, cyantraniliprole, andflubendiamide.

Groups 26 and 27 are unassigned in this version of the classificationscheme. Additionally, there is a Group UN that contains activeingredients of unknown or uncertain mode of action. This group includesthe following active ingredients, azadirachtin, benzoximate, bifenazate,bromopropylate, chinomethionat, cryolite, dicofol, pyridalyl, andpyrifluquinazon.

The term “pest” means an organism that is detrimental to humans, orhuman concerns (such as, crops, food, livestock, etc.), where saidorganism is from Phyla Arthropoda, Mollusca, or Nematoda. Particularexamples are ants, aphids, bed bugs, beetles, bristletails,caterpillars, cockroaches, crickets, earwigs, fleas, flies,grasshoppers, grubs, hornets, jassids, leafhoppers, lice, locusts,maggots, mealybugs, mites, moths, nematodes, plantbugs, planthoppers,psyllids, sawflies, scales, silverfish, slugs, snails, spiders,springtails, stink bugs, symphylans, termites, thrips, ticks, wasps,whiteflies, and wireworms.

Additional examples are pests in

(1) Subphyla Chelicerata, Myriapoda, and Hexapoda.

(2) Classes of Arachnida, Symphyla, and Insecta.

(3) Order Anoplura. A non-exhaustive list of particular genera includes,but is not limited to, Haematopinus spp., Hoplopleura spp., Linognathusspp., Pediculus spp., Polyplax spp., Solenopotes spp., andNeohaematopinis spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Haematopinus asini, Haematopinus suis,Linognathus setosus, Linognathus ovillus, Pediculus humanus capitis,Pediculus humanus humanus, and Pthirus pubis.

(4) Order Coleoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Acanthoscelides spp., Agriotes spp.,Anthonomus spp., Apion spp., Apogonia spp., Araecerus spp., Aulacophoraspp., Bruchus spp., Cerosterna spp., Cerotoma spp., Ceutorhynchus spp.,Chaetocnema spp., Colaspis spp., Ctenicera spp., Curculio spp.,Cyclocephala spp., Diabrotica spp., Dinoderus spp., Gnathocerus spp.,Hemicoelus spp., Heterobostruchus spp., Hypera spp., Ips spp., Lyctusspp., Megascelis spp., Meligethes spp., Mezium spp., Niptus spp.,Otiorhynchus spp., Pantomorus spp., Phyllophaga spp., Phyllotreta spp.,Ptinus spp., Rhizotrogus spp., Rhynchites spp., Rhynchophorus spp.,Scolytus spp., Sphenophorus spp., Sitophilus spp., Tenebrio spp., andTribolium spp. A non-exhaustive list of particular species includes, butis not limited to, Acanthoscelides obtectus, Agrilus planipennis,Ahasverus advena, Alphitobius diaperinus, Anoplophora glabripennis,Anthonomus grandis, Anthrenus verbasci, Anthrenus falvipes, Ataeniusspretulus, Atomaria linearis, Attagenus unicolor, Bothynoderespunctiventris, Bruchus pisorum, Callosobruchus maculatus, Carpophilushemipterus, Cassida vittata, Cathartus quadricollis, Cerotomatrifurcata, Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderusscalaris, Conoderus stigmosus, Conotrachelus nenuphar, Cotinis nitida,Crioceris asparagi, Cryptolestes ferrugineus, Cryptolestes pusillus,Cryptolestes turcicus, Cylindrocopturus adspersus, Deporaus marginatus,Dermestes lardarius, Dermestes maculatus, Epilachna varivestis,Euvrilletta peltata, Faustinus cubae, Hylobius pales, Hylotrupesbajulus, Hypera postica, Hypothenemus hampei, Lasioderma serricome,Leptinotarsa decemlineata, Limonius canus, Liogenys fuscus, Liogenyssuturalis, Lissorhoptrus oryzophilus, Lophocateres pusillus, Lyctusplanicollis, Maecolaspis joliveti, Melanotus communis, Meligethesaeneus, Melolontha melolontha, Necrobia rufipes, Oberea brevis, Oberealinearis, Oryctes rhinoceros, Oryzaephilus mercator, Oryzaephilussurinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga cuyabana,Polycaon stoutti, Popillia japonica, Prostephanus truncatus, Rhyzoperthadominica, Sitona lineatus, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum, Tenebroides mauritanicus,Tribolium castaneum, Tribolium confusum, Trogoderma granarium,Trogoderma variabile, Xestobium rufovillosum, and Zabrus tenebrioides.

(5) Order Dermaptera. A non-exhaustive list of particular speciesincludes, but is not limited to, Forficula auricularia.

(6) Order Blattaria. A non-exhaustive list of particular speciesincludes, but is not limited to, Blattella germanica, Blattellaasahinai, Blatta orientalis, Blatta lateralis, Parcoblattapennsylvanica, Periplaneta americana, Periplaneta australasiae,Periplaneta brunnea, Periplaneta fuliginosa, Pycnoscelus surinamensis,and Supella longipalpa.

(7) Order Diptera. A non-exhaustive list of particular genera includes,but is not limited to, Aedes spp., Agromyza spp., Anastrepha spp.,Anopheles spp., Bactrocera spp., Ceratitis spp., Chrysops spp.,Cochliomyia spp., Contarinia spp., Culex spp., Culicoides spp.,Dasineura spp., Delia spp., Drosophila spp., Fannia spp., Hylemya spp.,Liriomyza spp., Musca spp., Phorbia spp., Pollenia spp., Psychoda spp.,Simulium spp., Tabanus spp., and Tipula spp. A non-exhaustive list ofparticular species includes, but is not limited to, Agromyza frontella,Anastrepha suspensa, Anastrepha ludens, Anastrepha obliqua, Bactroceracucurbitae, Bactrocera dorsalis, Bactrocera invadens, Bactrocera zonata,Ceratitis capitata, Dasineura brassicae, Delia platura, Fanniacanicularis, Fannia scalaris, Gasterophilus intestinalis, Gracilliaperseae, Haematobia irritans, Hypoderma lineatum, Liriomyza brassicae,Liriomyza sativa, Melophagus ovinus, Musca autumnalis, Musca domestica,Oestrus ovis, Oscinella frit, Pegomya betae, Piophila casei, Psilarosae, Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletis mendax,Sitodiplosis mosellana, and Stomoxys calcitrans.

(8) Order Hemiptera. A non-exhaustive list of particular generaincludes, but is not limited to, Adelges spp., Aulacaspis spp.,Aphrophora spp., Aphis spp., Bemisia spp., Ceroplastes spp., Chionaspisspp., Chrysomphalus spp., Coccus spp., Empoasca spp., Euschistus spp.,Lepidosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp.,Nephotettix spp., Nezara spp., Nilaparvata spp., Philaenus spp.,Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp.,Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp.,Toxoptera spp., Trialeurodes spp., Triatoma spp., and Unaspis spp. Anon-exhaustive list of particular species includes, but is not limitedto, Acrostemum hilare, Acyrthosiphon pisum, Aleyrodes proletella,Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttulabiguttula, Aonidiella aurantii, Aphis fabae, Aphis gossypii, Aphisglycines, Aphis porni, Aulacorthum solani, Bactericera cockerelli,Bagrada hilaris, Bemisia argentifolii, Bemisia tabaci, Blissusleucopterus, Boisea trivittata, Brachycorynella asparagi, Brevenniarehi, Brevicoryne brassicae, Cacopsylla pyri, Cacopsylla pyricola,Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus, Cimexlectularius, Coccus pseudomagnoliarum, Dagbertus fasciatus, Dichelopsfurcatus, Diuraphis noxia, Diaphorina citri, Dysaphis plantaginea,Dysdercus suturellus, Edessa meditabunda, Empoasca vitis, Eriosomalanigerum, Erythroneura elegantula, Eurygaster maura, Euschistusconspersus, Euschistus heros, Euschistus servus, Halyomorpha halys,Helopeltis antonii, Hyalopterus pruni, Helopeltis antonii, Helopeltistheivora, Icerya purchasi, Idioscopus nitidulus, Jacobiasca formosana,Laodelphax striatellus, Lecanium corni, Leptocorisa oratorius,Leptocorisa varicomis, Lygus hesperus, Maconellicoccus hirsutus,Macrosiphum euphorbiae, Macrosiphum granarium, Macrosiphum rosae,Macrosteles quadrilineatus, Mahanarva frimbiolata, Megacopta cribraria,Metopolophium dirhodum, Mictis longicomis, Myzus persicae, Nasonoviaribisnigri, Nephotettix cincticeps, Neurocolpus longirostris, Nezaraviridula, Nilaparvata lugens, Paracoccus marginatus, Paratriozacockerelli, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis,Phylloxera vitifoliae, Physokermes piceae, Phytocoris califomicus,Phytocoris relativus, Piezodorus guildinii, Planococcus citri,Planococcus ficus, Poecilocapsus lineatus, Psallus vaccinicola,Pseudacysta perseae, Pseudococcus brevipes, Quadraspidiotus perniciosus,Rhopalosiphum maidis, Rhopalosiphum padi, Saissetia oleae, Scaptocoriscastanea, Schizaphis graminum, Sitobion avenae, Sogatella furcifera,Trialeurodes vaporariorum, Trialeurodes abutiloneus, Unaspis yanonensis,and Zulia entrerriana.

(9) Order Hymenoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Acromyrmex spp., Atta spp., Camponotusspp., Diprion spp., Dolichovespula spp., Formica spp., Monomorium spp.,Neodiprion spp., Paratrechina spp., Pheidole spp., Pogonomyrmex spp.,Polistes spp., Solenopsis spp., Technomyrmex, spp., Tetramorium spp.,Vespula spp., Vespa spp., and Xylocopa spp. A non-exhaustive list ofparticular species includes, but is not limited to, Athalia rosae, Attatexana, Caliroa cerasi, Cimbex americana, Iridomyrmex humilis,Linepithema humile, Mellifera Scutellata, Monomorium minimum, Monomoriumpharaonis, Neodiprion sertifer, Solenopsis invicta, Solenopsis geminata,Solenopsis molesta, Solenopsis richtery, Solenopsis xyloni, Tapinomasessile, and Wasmannia auropunctata.

(10) Order Isoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Coptotermes spp., Cornitermes spp.,Cryptotermes spp., Heterotermes spp., Kalotermes spp., Incisitermesspp., Macrotermes spp., Marginitermes spp., Microcerotermes spp.,Procornitermes spp., Reticulitermes spp., Schedorhinotermes spp., andZootermopsis spp. A non-exhaustive list of particular species includes,but is not limited to, Coptotermes acinaciformis, Coptotermescurvignathus, Coptotermes frenchi, Coptotermes formosanus, Coptotermesgestroi, Cryptotermes brevis, Heterotermes aureus, Heterotermes tenuis,Incisitermes minor, Incisitermes snyderi, Microtermes obesi,Nasutitermes corniger, Odontotermes formosanus, Odontotermes obesus,Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermesflavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermessantonensis, Reticulitermes speratus, Reticulitermes tibialis, andReticulitermes virginicus.

(11) Order Lepidoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Adoxophyes spp., Agrotis spp.,Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp.,Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp., Diatraeaspp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gortynaspp., Helicoverpa spp., Heliothis spp., Indarbela spp., Lithocolletisspp., Loxagrotis spp., Malacosoma spp., Nemapogon spp., Peridroma spp.,Phyllonorycter spp., Pseudaletia spp., Plutella spp., Sesamia spp.,Spodoptera spp., Synanthedon spp., and Yponomeuta spp. A non-exhaustivelist of particular species includes, but is not limited to, AchaeaJanata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbiacuneana, Amyelois transitella, Anacamptodes defectaria, Anarsialineatella, Anomis sabulifera, Anticarsia gemmatalis, Archipsargyrospila, Archips rosana, Argyrotaenia citrana, Autographa gamma,Bonagota cranaodes, Borbo cinnara, Bucculatrix thurberiella, Capuareticulana, Carposina niponensis, Chlumetia trans versa, Choristoneurarosaceana, Cnaphalocrocis medinalis, Conopomorpha cramerella, Corcyracephalonica, Cossus cossus, Cydia caryana, Cydia funebrana, Cydiamolesta, Cydia nigricana, Cydia pomonella, Darna diducta, Diaphanianitidalis, Diatraea saccharalis, Diatraea grandiosella, Earias insulana,Earias vittella, Ecdytolopha aurantianum, Elasmopalpus lignosellus,Ephestia cautella, Ephestia elutella, Ephestia kuehniella, Epinotiaaporema, Epiphyas postvittana, Erionota thrax, Estigmene acrea,Eupoecilia ambiguella, Euxoa auxiliaris, Galleria mellonella, Grapholitamolesta, Hedylepta indicata, Helicoverpa armigera, Helicoverpa zea,Heliothis virescens, Hellula undalis, Keiferia lycopersicella,Leucinodes orbonalis, Leucoptera coffeella, Leucoptera malifoliella,Lobesia botrana, Loxagrotis albicosta, Lymantria dispar, Lyonetiaderkella, Mahasena corbetti, Mamestra brassicae, Manduca sexta, Marucatestulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis,Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydiavesulia, Pandemis cerasana, Pandemis heparana, Papilio demodocus,Pectinophora gossypiella, Peridroma saucia, Perileucoptera coffeella,Phthorimaea operculella, Phyllocnistis citrella, Phyllonorycterblancardella, Pieris rapae, Plathypena scabra, Platynota idaeusalis,Plodia interpunctella, Plutella xylostella, Polychrosis viteana, Praysendocarpa, Prays oleae, Pseudaletia unipuncta, Pseudoplusia indudens,Rachiplusia nu, Scirpophaga incertulas, Sesamia inferens, Sesamianonagrioides, Setora nitens, Sitotroga cerealella, Sparganothispilleriana, Spodoptera exigua, Spodoptera frugiperda, Spodopteraeridania, Thecla basilides, Tinea pellionella, Tineola bisselliella,Trichoplusia ni, Tuta absoluta, Zeuzera coffeae, and Zeuzea pyrina.

(12) Order Mallophaga. A non-exhaustive list of particular generaincludes, but is not limited to, Anaticola spp., Bovicola spp.,Chelopistes spp., Goniodes spp., Menacanthus spp., and Trichodectes spp.A non-exhaustive list of particular species includes, but is not limitedto, Bovicola bovis, Bovicola caprae, Bovicola ovis, Chelopistesmeleagridis, Goniodes dissimilis, Goniodes gigas, Menacanthusstramineus, Menopon gallinae, and Trichodectes canis.

(13) Order Orthoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Melanoplus spp. and Pterophylla spp. Anon-exhaustive list of particular species includes, but is not limitedto, Acheta domesticus, Anabrus simplex, Gryllotalpa africana,Gryllotalpa australis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla,Locusta migratoria, Microcentrum retinerve, Schistocerca gregaria, andScudderia furcata.

(14) Order Psocoptera. A non-exhaustive list of particular speciesincludes, but is not limited to, sp. Liposcelis decolor, Liposcelisentomophila, Lachesilla quercus, and Trogium pulsatorium.

(15) Order Siphonaptera. A non-exhaustive list of particular speciesincludes, but is not limited to, Ceratophyllus gallinae, Ceratophyllusniger, Ctenocephalides canis, Ctenocephalides felis, and Pulex irritans.

(16) Order Thysanoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Caliothrips spp., Frankliniella spp.,Scirtothrips spp., and Thrips spp. A non-exhaustive list of particularspecies includes, but is not limited to, Caliothrips phaseoli,Frankliniella bispinosa, Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella schultzei, Frankliniella tritici,Frankliniella williamsi, Heliothrips haemorrhoidalis, Rhipiphorothripscruentatus, Scirtothrips citri, Scirtothrips dorsalis, Taeniothripsrhopalantennalis, Thrips hawaiiensis, Thrips nigropilosus, Thripsorientalis, Thrips palmi, and Thrips tabaci.

(17) Order Thysanura. A non-exhaustive list of particular generaincludes, but is not limited to, Lepisma spp. and Thermobia spp.

(18) Order Acarina. A non-exhaustive list of particular genera includes,but is not limited to, Acarus spp., Aculops spp., Argus spp., Boophilusspp., Demodex spp., Dermacentor spp., Epitrimerus spp., Eriophyes spp.,Ixodes spp., Oligonychus spp., Panonychus spp., Rhizoglyphus spp., andTetranychus spp. A non-exhaustive list of particular species includes,but is not limited to, Acarapis woodi, Acarus siro, Aceria mangiferae,Aculops lycopersici, Aculus pelekassi, Aculus schlechtendali, Amblyommaamericanum, Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentorvariabilis, Dermatophagoides pteronyssinus, Eotetranychus carpini,Liponyssoides sanguineus, Notoedres cati, Oligonychus coffeae,Oligonychus ilicis, Ornithonyssus bacoti, Panonychus citri, Panonychusulmi, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalussanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychusurticae, Tyrophagus longior, and Varroa destructor.

(19) Order Araneae. A non-exhaustive list of particular genera includes,but is not limited to, Loxosceles spp., Latrodectus spp., and Atrax spp.A non-exhaustive list of particular species includes, but is not limitedto, Loxosceles recluse, Latrodectus mactans, and Atrax robustus.

(20) Class Symphyla. A non-exhaustive list of particular speciesincludes, but is not limited to, Scutigerella immaculate.

(21) Subclass Collembola. A non-exhaustive list of particular speciesincludes, but is not limited to, Bourletiella hortensis, Onychiurusarmatus, Onychiurus fimetarius, and Sminthurus viridis.

(22) Phylum Nematoda. A non-exhaustive list of particular generaincludes, but is not limited to, Aphelenchoides spp., Belonolaimus spp.,Criconemella spp., Ditylenchus spp., Globodera spp., Heterodera spp.,Hirschmanniella spp., Hoplolaimus spp., Meloidogyne spp., Pratylenchusspp., and Radopholus spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Dirofilaria immitis, Globodera pallida,Heterodera glycines, Heterodera zeae, Meloidogyne incognita, Meloidogynejavanica, Onchocerca volvulus, Pratylenchus penetrans, Radopholussimilis, and Rotylenchulus reniformis.

(23) Phylum Mollusca. A non-exhaustive list of particular speciesincludes, but is not limited to, Arion vulgaris, Cornu aspersum,Deroceras reticulatum, Limax flavus, Milax gagates, and Pomaceacanaliculata.

A particularly preferred pest group to control is sap-feeding pests.Sap-feeding pests, in general, have piercing and/or sucking mouthpartsand feed on the sap and inner plant tissues of plants. Examples ofsap-feeding pests of particular concern to agriculture include, but arenot limited to, aphids, leafhoppers, moths, scales, thrips, psyllids,mealybugs, stinkbugs, and whiteflies. Specific examples of Orders thathave sap-feeding pests of concern in agriculture include but are notlimited to, Anoplura and Hemiptera. Specific examples of Hemiptera thatare of concern in agriculture include, but are not limited to,Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia spp., Coccus spp.,Euschistus spp., Lygus spp., Macrosiphum spp., Nezara spp., andRhopalosiphum spp.

Another particularly preferred pest group to control is chewing pests.Chewing pests, in general, have mouthparts that allow them to chew onthe plant tissue including roots, stems, leaves, buds, and reproductivetissues (including, but not limited to flowers, fruit, and seeds).Examples of chewing pests of particular concern to agriculture include,but are not limited to, caterpillars, beetles, grasshoppers, andlocusts. Specific examples of Orders that have chewing pests of concernin agriculture include but are not limited to, Coleoptera andLepidoptera. Specific examples of Coleoptera that are of concern inagriculture include, but are not limited to, Anthonomus spp., Cerotomaspp., Chaetocnema spp., Colaspis spp., Cyclocephala spp., Diabroticaspp., Hypera spp., Phyllophaga spp., Phyllotreta spp., Sphenophorusspp., Sitophilus spp.

The phrase “pesticidally effective amount” means the amount of apesticide needed to achieve an observable effect on a pest, for example,the effects of necrosis, death, retardation, prevention, removal,destruction, or otherwise diminishing the occurrence and/or activity ofa pest in a locus. This effect may come about when pest populations arerepulsed from a locus, pests are incapacitated in, or around, a locus,and/or pests are exterminated in, or around, a locus. Of course, acombination of these effects can occur. Generally, pest populations,activity, or both are desirably reduced more than fifty percent,preferably more than 90 percent, and most preferably more than 99percent. In general, a pesticidally effective amount, for agriculturalpurposes, is from about 0.0001 grams per hectare to about 5000 grams perhectare, preferably from about 0.0001 grams per hectare to about 500grams per hectare, and it is even more preferably from about 0.0001grams per hectare to about 50 grams per hectare.

DETAILED DESCRIPTION OF THIS DISCLOSURE

This document discloses molecules of Formula One

wherein:

(A) Ar¹ is selected from the group consisting of furanyl, phenyl,pyridazinyl, pyridyl, pyrimidinyl, or thienyl,

-   -   wherein each furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl,        and thienyl may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy substituent may be        optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(B) Het is a 5- or 6-membered, saturated or unsaturated, heterocyclicring, containing one or more heteroatoms independently selected fromnitrogen, sulfur, or oxygen, and where Ar¹ and 0 are not ortho to eachother, but may be meta or para, such as, for a five-membered ring theyare 1,3, and for a 6-membered ring they are either 1,3 or 1,4,

-   -   wherein each heterocyclic ring may be optionally substituted        with one or more substituents independently selected from the        group consisting of H, F, Cl, Br, I, CN, NO₂, oxo, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—,        —(C₁-C₄)alkyl, S(O)_(n)—, —(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy substituent may be        optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—, —(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(C) L¹ is selected from the group consisting of O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-O, O—(C₁-C₄)haloalkyl,(C₁-C₄)haloalkyl-O, O—(C₃-C₈)cycloalkyl, (C₃-C₈)cycloalkyl-O,O—(C₁-C₄)haloalkoxy, (C₁-C₄)haloalkoxy-O, O—(C₂-C₆)alkenyl,(C₂-C₆)alkenyl-O, O—(C₂-C₆)alkynyl, and O—(C₂-C₆)alkynyl,

-   -   wherein each alkyl, haloalkyl, cycloalkyl, alkenyl, and alkynyl        may be optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, and (C₂-C₆)alkynyl;

(D) Ar² is selected from the group consisting of furanyl, phenyl,pyridazinyl, pyridyl, pyrimidinyl, or thienyl,

-   -   wherein each furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl,        and thienyl may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy substituent may be        optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(E) R¹⁵ is selected from the group consisting of H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, C(O)—NR^(x)R^(y), C(O)-phenyl,(C₁-C₄)alkyl-NR^(x)R^(y), C(O)O—(C₁-C₄)alkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, and phenyl may        be optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, oxo, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(F) Q¹ is selected from the group consisting of O and S;

(G) Q² is selected from the group consisting of O and S;

(H) R¹⁶ is selected from the group consisting of (K), H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,(C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl, C(O)-(Het-1), (Het-1),(C₁-C₄)alkyl-(Het-1), (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-C(O)-(Het-1),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(NR^(x)R^(y))—C(O)OH,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(N(R^(x))—C(O)O—(C₁-C₄)alkyl)-C(O)OH,(C₁-C₄)alkyl-C(O)-(Het-1)-C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₃-C₈)cycloalkyl, (C₁-C₄)alkyl-OC(O)-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-NR^(x)R^(y), (C₁-C₄)alkyl-S(O)_(n)-(Het-1), and(C₁-C₄)alkyl-O-(Het-1),

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        (Het-1) may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)OH, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl), phenyl, phenoxy,        Si((C₁-C₄)alkyl)₃, S(O)_(n)—NR^(x)R^(y), and (Het-1);

(I) R¹⁷ is selected from the group consisting of (K), H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,(C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl, C(O)-(Het-1), (Het-1),(C₁-C₄)alkyl-(Het-1), (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-C(O)-(Het-1),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(NR^(x)R^(y))—C(O)OH,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(N(R^(x))—C(O)O—(C₁-C₄)alkyl)-C(O)OH,(C₁-C₄)alkyl-C(O)-(Het-1)-C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₃-C₈)cycloalkyl, (C₁-C₄)alkyl-OC(O)-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-NR^(x)R^(y), (C₁-C₄)alkyl-S(O)_(n)-(Het-1), and(C₁-C₄)alkyl-O-(Het-1),

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        (Het-1) may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)OH, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy,        Si((C₁-C₄)alkyl)₃, S(O)_(n)—NR^(x)R^(y), and (Het-1);

(J) L² is selected from the group consisting of (C₃-C₈)cycloalkyl,phenyl, (C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl,(C₂-C₆)alkenyl-O-phenyl, (Het-1), (C₁-C₄)alkyl-(Het-1), and(C₁-C₄)alkyl-O-(Het-1),

-   -   wherein each alkyl, cycloalkyl, alkenyl, phenyl, and (Het-1) may        be optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₁-C₄)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl, O—(C₁-C₄)alkyl,        S—(C₁-C₄)alkyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy, and        (Het-1),    -   wherein each alkyl, cycloalkyl, alkenyl, phenyl, and (Het-1)        substituent may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)H,        C(O)—NR^(x)R^(y), (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl,        C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,        C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,        C(O)O—(C₁-C₄)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, O—(C₁-C₄)alkyl, S—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy, and        (Het-1);

(K) R¹⁶ and R¹² along with C^(x)(Q²)(N^(x)), form a 4- to 7-memberedsaturated or unsaturated, heterocyclic ring, which may further containone or more heteroatoms selected from the group consisting of nitrogen,sulfur, and oxygen,

-   -   wherein each heterocyclic ring may be optionally substituted        with one or more substituents independently selected from the        group consisting of oxo, R¹⁸, and R¹⁹,    -   wherein R¹⁸ and R¹⁹ are each independently selected from the        group consisting of H, F, Cl, Br, I, CN, NO₂, oxo, thioxo,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl,        C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,        C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,        C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and (Het-1);

(L) R^(x) and R^(y) are each independently selected from the groupconsisting of H, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, and phenyl,

-   -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, and phenyl may be optionally substituted with        one or more substituents independently selected from the group        consisting of H, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)H,        C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,        C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,        C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and (Het-1);

(M) (Het-1) is a 5- or 6-membered, saturated or unsaturated,heterocyclic ring, containing one or more heteroatoms independentlyselected from the group consisting of nitrogen, sulfur, or oxygen,

-   -   wherein each heterocyclic ring may be optionally substituted        with one or more substituents independently selected from the        group consisting of H, F, Cl, Br, I, CN, NO₂, oxo, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy substituent may be        optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(N) n are each independently 0, 1, or 2; and

N-oxides, agriculturally acceptable acid addition salts, saltderivatives, solvates, crystal polymorphs, isotopes, resolvedstereoisomers, and tautomers, of the molecules of Formula One.

The molecules of Formula One may exist in different geometric or opticalisomeric or different tautomeric forms. One or more centers of chiralitymay be present in which case molecules of Formula One may be present aspure enantiomers, mixtures of enantiomers, pure diastereomers ormixtures of diastereomers. It will be appreciated by those skilled inthe art that one stereoisomer may be more active than the otherstereoisomers. Individual stereoisomers may be obtained by knownselective synthetic procedures, by conventional synthetic proceduresusing resolved starting materials, or by conventional resolutionprocedures. There may be double bonds present in the molecule, in whichcase compounds of Formula One may exist as single geometric isomers (cisor trans, E or Z) or mixtures of geometric isomers (cis and trans, E andZ). Centers of tautomerisation may be present. This disclosure coversall such isomers, tautomers, and mixtures thereof, in all proportions.The structures disclosed in the present disclosure are drawn in only onegeometric form for clarity, but are intended to represent all geometricforms of the molecule.

In another embodiment Ar¹ is (1a)

wherein:

-   -   (1) R¹, R², R⁴, and R⁵ are each independently H; and    -   (2) R³ is (C₁-C₄)haloalkoxy.

This embodiment may be used in combination with the other embodiments ofHet, L¹, Ar², R¹⁵, Q¹, Q², R¹⁶, R¹⁷, and L².

In another embodiment Ar¹ is (1a), wherein R³ is OCF₃. This embodimentmay be used in combination with the other embodiments of R¹, R², R⁴, R⁵,Het, L¹, Ar², R¹⁵, Q¹, Q², R¹⁶, R¹⁷, and L².

In another embodiment Het is (1b)

wherein R⁶ is H. This embodiment may be used in combination with theother embodiments of Ar¹, L¹, Ar², R¹⁵, Q¹, Q², R¹⁶, R¹⁷, and L².

In another embodiment L¹ is (1c)

wherein R⁷ and R⁹ are each independently H. This embodiment may be usedin combination with the other embodiments of Ar¹, Het, Ar², R¹⁵, Q¹, Q²,R¹⁶, R¹⁷, and L².

In another embodiment L¹ is (1d)

wherein R⁸ and R¹⁰ are each independently H. This embodiment may be usedin combination with the other embodiments of Ar¹, Het, Ar², R¹⁵, Q¹, Q²,R¹⁶, R¹⁷, and L².

In another embodiment Ar² is (1e)

wherein:

-   -   (1) R¹¹ and R¹² are each independently H or F;    -   (2) X¹ is N or CR¹³, wherein R¹³ is H, F, Cl, (C₁-C₄)alkyl, or        (C₁-C₄)alkoxy; and    -   (3) X² is N or CR¹⁴, wherein R¹⁴ is H, F, Cl, or (C₁-C₄)alkoxy.

This embodiment may be used in combination with the other embodiments ofAr¹, Het, L¹, R¹⁸, Q¹, Q², R¹⁶, R¹⁷, and L².

In another embodiment Ar² is (1e), wherein R¹³ is CH₃ or OCH₃. Thisembodiment may be used in combination with the other embodiments of Ar¹,Het, L¹, R¹¹, R¹², X², Q¹, Q², R¹⁶, R¹⁷, and L².

In another embodiment Ar² is (1e), wherein R¹⁴ is OCH₃. This embodimentmay be used in combination with the other embodiments of Ar¹, Het, L¹,R¹¹, R¹², X¹, Q¹, Q², R¹⁶, R¹⁷, and L².

In another embodiment R¹⁵ is H. This embodiment may be used incombination with the other embodiments of Ar¹, Het, L¹, Ar², Q¹, Q²,R¹⁶, R¹⁷, and L².

In another embodiment Q¹ is O. This embodiment may be used incombination with the other embodiments of Ar¹, Het, L¹, Ar², R¹⁵, Q²,R¹⁶, R¹⁷, and L².

In another embodiment Q² is S. This embodiment may be used incombination with the other embodiments of Ar¹, Het, L¹, Ar², R¹⁵, Q¹,R¹⁶, R¹⁷, and L².

In another embodiment L² is (1f)

wherein:

-   -   (1) R²⁰ is (C₁-C₄)alkyl or (C₁-C₄)alkyl-O—(C₁-C₄)alkyl;    -   (2) R²¹ is H;    -   (3) R²² is H or F;    -   (4) R²³ is (C₁-C₄)alkyl; and    -   (5) R²⁴ is H.

This embodiment may be used in combination with the other embodiments ofAr¹, Het, L¹, Ar², R¹⁵, Q¹, Q², R¹⁶, and R¹⁷.

In another embodiment L² is (1f), wherein R²⁰ is CH₂CH₂CH₃, CH(CH₃)₂,CH₂OCH₃, or CH(CH₃)OCH₃. This embodiment may be used in combination withthe other embodiments of Ar¹, Het, L¹, Ar², Q¹, Q², R¹⁶, R¹⁷, R²¹, R²²,R²³, and R²⁴.

In another embodiment L² is (1f), wherein R²³ is CH₃. This embodimentmay be used in combination with the other embodiments of Ar¹, Het, L¹,Ar², Q¹, Q², R¹⁶, R¹⁷, R²⁰, R²¹, R²², and R²⁴.

In another embodiment R¹⁶ and R¹⁷ along with C^(x)(Q²)(N^(x)), are (1g)

wherein R¹⁸ and R¹⁹ are each independently H. This embodiment may beused in combination with the other embodiments of Ar¹, Het, L¹, Ar²,R¹⁵, Q¹, and L².

In another embodiment . . .

(A) Ar¹ is (1a)

-   -   wherein, R¹, R², R³, R⁴, and R⁵ are each independently selected        from the group consisting of H, F, Cl, Br, I, CN, NO₂,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy may be optionally        substituted with one or more substituents independently selected        from the group consisting of H, F, Cl, Br, I, CN, NO₂,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(B) Het is (1b)

-   -   wherein, R⁶ may be optionally substituted with a substituent        selected from the group consisting of H, F, Cl, Br, I, CN, NO₂,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy may be optionally        substituted with one or more substituents independently selected        from the group consisting of H, F, Cl, Br, I, CN, NO₂,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(C) 12 is selected from the group consisting of

-   -   wherein, R⁷, R⁸, R⁹, and R¹⁰ are each independently selected        from the group consisting of H, CN, NO₂, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, and (C₂-C₆)alkynyl;

(D) Ar² is (1e)

-   -   wherein:    -   (1) X¹ is selected from the group consisting of N and CR¹³,    -   (2) X² is selected from the group consisting of N and CR¹⁴, and    -   (3) R¹¹, R¹², R¹³, and R¹⁴ are each independently selected from        the group consisting of H, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy may be optionally        substituted with one or more substituents independently selected        from the group consisting of H, F, Cl, Br, I, CN, NO₂,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(E) R¹⁵ is selected from the group consisting of H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, C(O)—NR^(x)R^(y), C(O)-phenyl,(C₁-C₄)alkyl-NR^(x)R^(y), C(O)O—(C₁-C₄)alkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, and phenyl may        be optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, oxo, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy;

(F) Q¹ is selected from the group consisting of O and S;

(G) Q² is selected from the group consisting of O and S;

(H) R¹⁶ is selected from the group consisting of (K), H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,(C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl, C(O)-(Het-1), (Het-1),(C₁-C₄)alkyl-(Het-1), (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-C(O)-(Het-1),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(NR^(x)R^(y))—C(O)OH,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(N(R^(x))—C(O)O—(C₁-C₄)alkyl)-C(O)OH,(C₁-C₄)alkyl-C(O)-(Het-1)-C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₃-C₈)cycloalkyl, (C₁-C₄)alkyl-OC(O)-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-NR^(x)R^(y), (C₁-C₄)alkyl-S(O)_(n)-(Het-1), and(C₁-C₄)alkyl-O-(Het-1),

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        (Het-1) may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)OH, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl), phenyl, phenoxy,        Si((C₁-C₄)alkyl)₃, S(O)_(n)—NR^(x)R^(y), and (Het-1);

(I) R¹⁷ is selected from the group consisting of (K), H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,(C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl, C(O)-(Het-1), (Het-1),(C₁-C₄)alkyl-(Het-1), (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-C(O)-(Het-1),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(NR^(x)R^(y))—C(O)OH,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(N(R^(x))—C(O)O—(C₁-C₄)alkyl)-C(O)OH,(C₁-C₄)alkyl-C(O)-(Het-1)-C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁—C₄)alkyl-OC(O)—(C₃-C₈)cycloalkyl, (C₁-C₄)alkyl-OC(O)-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-NR^(x)R^(y), (C₁-C₄)alkyl-S(O)_(n)-(Het-1), and(C₁-C₄)alkyl-O-(Het-1),

-   -   wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and        (Het-1) may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)OH, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy,        Si((C₁-C₄)alkyl)₃, S(O)_(n)—NR^(x)R^(y), and (Het-1);

(J) L² is (1f)

-   -   wherein, R²⁰, R²¹, R²², R²³, and R²⁴ are each independently        selected from the group consisting of H, F, Cl, Br, I, CN, NO₂,        NR^(x)R^(y), (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—        (C₃-C₈)cycloalkyl, C(O)O—(C₁-C₄)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, O—(C₁-C₄)alkyl, S—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy, and        (Het-1),    -   wherein each alkyl, cycloalkyl, alkenyl, phenyl, and (Het-1)        substituent may be optionally substituted with one or more        substituents independently selected from the group consisting of        H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)H,        C(O)—NR^(x)R^(y), (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl,        C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,        C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,        C(O)O—(C₁-C₄)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, O—(C₁-C₄)alkyl, S—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy, and        (Het-1);

(K) R¹⁶ and R¹² along with C^(x)(Q²)(N^(x)), is (1g)

-   -   wherein, R¹⁸ and R¹⁹ are each independently selected from the        group consisting of H, F, Cl, Br, I, CN, NO₂, oxo, thioxo,        (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,        (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,        (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl,        C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,        C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,        C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and (Het-1);

(L) R^(x) and R^(y) are each independently selected from the groupconsisting of H, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, and phenyl,

-   -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, and phenyl may be optionally substituted with        one or more substituents independently selected from the group        consisting of H, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)H,        C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,        C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,        C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl,        C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,        (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and (Het-1);

(M) (Het-1) is a 5- or 6-membered, saturated or unsaturated,heterocyclic ring, containing one or more heteroatoms independentlyselected from the group consisting of nitrogen, sulfur, or oxygen,

-   -   wherein each heterocyclic ring may be optionally substituted        with one or more substituents independently selected from the        group consisting of H, F, Cl, Br, I, CN, NO₂, oxo, (C₁-C₄)alkyl,        (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,        (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,        S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,        OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy,    -   wherein each alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy,        alkenyl, alkynyl, phenyl, and phenoxy substituent may be        optionally substituted with one or more substituents        independently selected from the group consisting of H, F, Cl,        Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,        (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,        (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl,        S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,        OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),        (C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl,        C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,        C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,        C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy; and

(N) n are each independently 0, 1, or 2.

In another embodiment

(A) Ar¹ is (1a)

-   -   wherein, R¹, R², R³, R⁴, and R⁵ are each independently selected        from the group consisting of H and (C₁-C₄)haloalkoxy;

(B) Het is (1b)

-   -   wherein, R⁶ is H;

(C) L¹ is selected from the group consisting of

-   -   wherein, R², R⁸, R⁹, and R¹⁹ are each independently H;

(D) Ar² is (1e)

-   -   wherein:    -   (1) X¹ is selected from the group consisting of N and CR¹³,    -   (2) X² is selected from the group consisting of N and CR¹⁴, and    -   (3) R¹¹, R¹², R¹³, and R¹⁴ are each independently selected from        the group consisting of H, F, Cl, (C₁-C₄)alkyl, and        (C₁-C₄)alkoxy;

(E) R¹⁸ is H;

(F) Q¹ is O;

(G) Q² is S;

(H) R¹⁶ is (K);

(I) R¹⁷ is (K);

(J) L² is (1f)

-   -   wherein, R²⁰, R²¹, R²², R²³, and R²⁴ are each independently        selected from the group consisting of H, F, (C₁-C₄)alkyl, and        (C₁-C₄)alkyl-O—(C₁-C₄)alkyl; and

(K) R¹⁶ and R¹⁷ along with C^(x)(Q²)(N^(x)), is (1g)

-   -   wherein, R¹⁸ and R¹⁹ are each independently H.

In another embodiment

(A) Ar¹ is (1a)

-   -   wherein, R¹, R², R³, R⁴, and R⁵ are each independently selected        from the group consisting of H and OCF₃;

(B) Het is (1b)

-   -   wherein, R⁶ is H;

(C) L¹ is selected from the group consisting of

-   -   wherein, R⁷, R⁸, R⁹, and R¹⁰ are each independently H;

(D) Ar² is (1e)

-   -   wherein:    -   (1) X¹ is selected from the group consisting of N and CR¹³,    -   (2) X² is selected from the group consisting of N and CR¹⁴, and    -   (3) R¹¹, R¹², R¹³, and R¹⁴ are each independently selected from        the group consisting of H, F, Cl, CH₃, and OCH₃;

(E) R¹⁵ is H;

(F) Q¹ is O;

(G) Q² is S;

(H) R¹⁶ is (K);

(I) R¹⁷ is (K);

(J) L² is (1f)

-   -   wherein, R²⁰, R²¹, R²², R²³, and R²⁴ are each independently        selected from the group consisting of H, F, CH₃, CH₂CH₂CH₃,        CH(CH₃)₂, CH₂OCH₃, and CH(CH₃)OCH₃; and

(K) R¹⁶ and R¹⁷ along with C^(x)(Q²)(N^(x)), is (1g)

-   -   wherein, R¹⁸ and R¹⁹ are each independently H.

Preparation of Molecules of Formula One

Many of the molecules of Formula One may be depicted in two or moretautomeric forms such as when R¹⁶ and R¹⁷ are H (Scheme TAU). For thesake of simplifying the schemes, all molecules have been depicted asexisting as a single tautomer. Any and all energetically accessibletautomers are included within the scope of this Formula One, and noinference should be made as to whether the molecule exists as thetautomeric form in which it is drawn.

The molecules of Formula One will generally have a molecular mass ofabout 400 Daltons to about 1200 Daltons.

Preparation of Acyl Azides

Molecules of Formula One disclosed herein may be prepared from thecorresponding isocyanates 1-2, wherein Ar¹, Het, L¹, and Ar² are aspreviously disclosed. In some cases these isocyanates are not isolated,but are instead generated in situ from a suitable precursor and useddirectly in the preparation of molecules of Formula One. One suchsuitable precursor are amines 1-1, wherein Ar¹, Het, L¹, and Ar² are aspreviously disclosed, which may be converted into isocyanates 1-2 byusing one of several common reagents such as phosgene, diphosgene, ortriphosgene, in a mixed solvent system such as dichloromethane and wateror diethyl ether and water, in the presence of a base such as sodiumbicarbonate or triethylamine, at temperatures from about −10° C. toabout 50° C. (Scheme 1, step a).

Alternatively, the isocyanates may be generated via the Curtiusrearrangement of acyl azides 1-4, wherein Ar¹, Het, L¹, and Ar² are aspreviously disclosed, which is, in turn, prepared from the correspondingcarboxylic acids 1-3, wherein Ar¹, Het, L¹, and Ar² are as previouslydisclosed. Formation of acyl azides 1-4 may occur either by treatment ofthe acid with ethyl chloroformate and sodium azide in the presence of anamine base such as triethylamine, or with diphenylphosphoryl azide inthe presence of an amine base such as trimethylamine (Scheme 1, step b).Acyl azides 1-4 are then made to undergo a thermally-induced Curtiusrearrangement, leading to the corresponding isocyanates 1-2. Dependingon the nature of the particular acyl azide, this rearrangement may occurspontaneously at room temperature, or it may require heating from 40° C.to about 100° C. in a solvent, such as toluene, acetonitrile, or anethereal solvent such as dioxane or tetrahydrofuran. Acyl azides 1-4 arenot always fully characterized, but may simply be heated directlywithout characterization, to generate isocyanates 1-2.

Preparation of Linear Biurets

Isolated isocyanates 1-2 or isocyanates 1-2 prepared in situ fromcorresponding acyl azides 1-4 via the Curtius rearrangement, may betreated directly with ureas 2-1, wherein Q² and L² are as previouslydisclosed, in the presence of about 0.1 equivalents to about 2equivalents of an inorganic base such as cesium carbonate or sodiumhydride, resulting in the formation of biurets 2-2, wherein Ar¹, Het,L¹, Ar², Q², and L² are as previously disclosed (Scheme 2, step a). Thereaction can be performed at temperatures from about 0° C. to about 100°C., preferably from about 20° C. to about 80° C., in an aprotic solventor solvent mixture chosen from acetonitrile, acetone, toluene,tetrahydrofuran, dichloroethane, dichloromethane, or mixtures thereof,but use of acetonitrile is preferred.

Preparation of Substituted Linear Biurets

Linear biurets 2-2 may be treated with R¹⁶-halo, wherein R¹⁶ is aspreviously disclosed, in a protic solvent, such as ethanol, in thepresence of a base, such as sodium acetate, at temperatures from about0° C. to about 60° C., to yield substituted linear biurets 3-1, whereinAr¹, Het, L¹, Ar², Q², R¹⁶, and L² areas previously disclosed (Scheme 3,step a).

Preparation of Cyclic Biurets

Linear biurets 2-2 generated in situ may be converted directly withoutpurification into a variety of cyclized analogs (Scheme 4), or they canbe isolated from the reaction medium prior to cyclization. Cyclizationmay be achieved by treatment with an α-halo ester such as methylbromoacetate to form 2-imino 1,3-chalcogenazolin-4-ones 4-1, whereinAr¹, Het, L¹, Ar², Q², R¹⁸, R¹⁹, and L² are as previously disclosed(Scheme 4, step a); vicinal dihalides such as 1-bromo-2-chloroethane or1,2-dichloroethane, to form 2-imino-1,3-chalogenazolines 4-2, whereinAr¹, Het, L¹, Ar², Q², R¹⁸, R¹⁹, and L² are as previously disclosed(Scheme 4, step b); α-halo ketones such as chloroacetone to form2-imino-1,3-chalcogenazoles 4-3, wherein Ar¹, Het, L¹, Ar², Q², R¹⁸,R¹⁹, and L² are as previously disclosed (Scheme 4, step c);1,3-dihalopropanes such as 1-bromo-3-chloro-propane to form2-imino-1,3-chalcogenazinanes 4-4, wherein Ar¹, Het, L¹, Ar², Q², R¹⁸,R¹⁹, and L² are as previously disclosed (Scheme 4, step d); orα,β-unsaturated acid chlorides such as acryloyl chloride to form2-imino-1,3-chalcogenazinones 4-5, wherein Ar¹, Het, L¹, Ar², Q², R¹⁸,R¹⁹, and L² are as previously disclosed (Scheme 4, step e). With step ain Scheme 4, the use of sodium acetate in a protic solvent such asethanol or methanol, at temperatures ranging from about 20° C. to about70° C. is preferred. With step b in Scheme 4, the use of an inorganicbase such as potassium carbonate in a solvent such as acetonitrile or(preferably) 2-butanone, at a temperature between about 0° C. and about80° C., is preferred.

An alternative method for preparing cyclic biurets is described inScheme 5. 2-Imino-1,3-chalcogenazoheterocycles 5-1, whereinC^(x)(Q²)(N^(x)), R¹⁶, R¹⁷, and L² are as previously disclosed, may betreated directly with isolated isocyanates 1-2 or isocyanates 1-2prepared in situ from corresponding acyl azides 1-4 via the Curtiusrearrangement, either in the absence of base or in the presence of about0.1 equivalents to about 2 equivalents of an inorganic base, such ascesium carbonate or sodium hydride, to form cyclic thiobiurets 5-2,wherein Ar¹, Het, L¹, Ar₂, Q₂, R₁₆, R₁₇, and L² are as previouslydisclosed (Scheme 5, step a). The reaction may be performed attemperatures from about 0° C. to about 100° C., preferably from about20° C. to about 80° C., in an aprotic solvent or solvent mixture chosenfrom acetonitrile, acetone, toluene, tetrahydrofuran,1,2-dichloroethane, dichloromethane, or mixtures thereof, but use ofacetonitrile is preferred. Cyclic biurets 4-1, 4-2, 4-3, 4-4, and 4-5,wherein L¹ contains an olefin, may be reduced by treatment with hydrogenin the presence of a transition metal catalyst, such as palladium oncarbon or platinum(IV) oxide.

Alternatively, 2-imino-1,3-chalcogenazoheterocycles 5-1 may be reactedwith 4-nitrophenyl chloroformate, forming 4-nitrophenyl carbamates 5-2,wherein C^(x)(Q²)(N^(x)), R¹⁶, R¹⁷, and L² are as previously disclosed(Scheme 5, step b). This reaction may be conducted with equimolarquantities of 2-imino-1,3-chalcogenazoheterocycles 5-1 and thechloroformate, in a polar aprotic solvent, such as tetrahydrofuran,dioxane, or acetonitrile, in the presence of from about 0.1 equivalentsto about 2 equivalents of an inorganic base, such as cesium carbonate orpotassium carbonate, preferably at about room temperature. 4-Nitrophenylcarbamates 5-2 may be isolated by filtration and concentration of thefiltrate, or 4-nitrophenyl carbamates 5-2 may be used directly (Scheme5, step c). Treatment of 4-nitrophenyl carbamates 5-2 with amines 1-1may generate cyclic thiobiurets 5-2. Step c may also be conducted in thepresence of an inorganic base, such as cesium carbonate or potassiumcarbonate, from about 0.1 equivalents to about 2 equivalents, preferablyabout 1 equivalents to about 1.2 equivalents, at temperatures from about0° C. to about 100° C., preferably about room temperature. Cyclicbiurets 5-2, wherein L¹ contains an olefin, may be reduced by treatmentwith hydrogen in the presence of a transition metal catalyst, such aspalladium on carbon or platinum(IV) oxide.

An alternative method for preparing cyclic biurets is described inScheme 6. Amines 1-1 may be reacted with 4-nitrophenyl chloroformate,forming 4-nitrophenyl carbamates 6-1, wherein Ar¹, Het, L¹, and Ar² areas previously disclosed (Scheme 6, step a). This reaction may beconducted with equimolar quantities of amines 1-1 and the chloroformate,in a polar aprotic solvent, such as tetrahydrofuran, dioxane, oracetonitrile, in the presence of from about 0.1 equivalents to about 2equivalents of an inorganic base, such as cesium carbonate or potassiumcarbonate, preferably at about room temperature. 4-Nitrophenylcarbamates 6-1 may be isolated by filtration and concentration of thefiltrate, or 4-nitrophenyl carbamates 6-1 may be used directly (Scheme6, step b). Treatment of 4-nitrophenyl carbamates 6-1 with2-imino-1,3-chalcogenazoheterocycles 5-1 may generate cyclic thiobiurets5-2. This reaction may be conducted with equimolar quantities ofnitrophenyl carbamates 6-1 and 2-imino-1,3-chalcogenazoheterocycles 5-1,in a polar aprotic solvent, acetonitrile, in the presence of from about0.1 equivalents to about 2 equivalents of an inorganic base, such ascesium carbonate or potassium carbonate, and about 2 equivalents of anorganic base, such as N,N-diisopropylethylamine, preferably at aboutroom temperature. Cyclic biurets 5-2, wherein L¹ contains an olefin, maybe reduced by treatment with hydrogen in the presence of a transitionmetal catalyst, such as palladium on carbon or platinum(IV) oxide.

An additional method for preparing cyclic biurets is described in Scheme7. Treatment of carbamates 7-1, wherein Ar¹, Het, L¹, and Ar² are aspreviously disclosed, with 2-imino-1,3-chalcogenazoheterocycles 5-1 maygenerate cyclic thiobiurets 5-2. This reaction may be conducted in aaprotic solvent such as toluene, at temperatures from about 80° C. toabout 140° C. in a sealed tube (Scheme 7, step a). Cyclic biurets 5-2,wherein L¹ contains an olefin, may be reduced by treatment with hydrogenin the presence of a transition metal catalyst, such as palladium oncarbon or platinum(IV) oxide.

Preparation of Carboxylic Acids

Methods for preparation of carboxylic acids 8-4, wherein Ar¹ and Ar² areas previously disclosed, required for preparation of molecules ofFormula One are described in Scheme 8. Hydrazines 8-1, wherein Ar¹ is aspreviously disclosed, may be treated with urea in the presence of anacid such as para-toluenesulfonic acid monohydrate, in a solvent such aschlorobenzene, at temperatures from about 130° C. to about 150° C., fortimes ranging from about 1 hour to 3 hours. Further treatment withchlorosulfonic acid at temperatures from about 70° C. to about 90° C.may provide triazoles 8-2, wherein Ar¹ is as previously disclosed(Scheme 8, step a).

Triazoles 8-2 may be treated with Halo-CH₂—Ar²—C(O)O(C₁-C₄)alkyl,wherein Halo are Cl, Br, or I and Ar² is as previously disclosed, and anadditive such as tetrabutylammonium iodide, in the presence of a base,such as potassium carbonate, in a polar aprotic solvent, such asacetonitrile, at temperatures from about 50° C. to about 90° C., to formesters 8-3, wherein Ar¹ and Ar² are as previously disclosed (Scheme 8,step b). Esters 8-3 may be treated with a metal hydroxide such aspotassium hydroxide, sodium hydroxide, or lithium hydroxide, in asolvent such as tetrahydrofuran, methanol, water, or mixtures thereof,to form carboxylic acids 8-4 (Scheme 8, step c).

Methods for preparation of carboxylic acids 9-6, wherein Ar¹ and Ar² areas previously disclosed, required for preparation of molecules ofFormula One are described in Scheme 9. Triazoles 9-1 may be treated witha boronic acid such as Ar¹—B(OH)₂, wherein Ar¹ is as previouslydisclosed, in the presence of a copper catalyst such as copper(II)acetate, and a base such as pyridine, in a solvent such asdichloromethane, at temperatures from about 15° C. to about 30° C., toform esters 9-2, wherein Ar¹ is as previously disclosed (Scheme 9, stepa). Reduction of esters 9-2 with a hydride source such as lithiumaluminum hydride, in a polar aprotic solvent such as tetrahydrofuran, attemperatures from about −10° C. to about 40° C. may provide alcohols9-3, wherein Ar¹ is as previously disclosed (Scheme 9, step b). Alcohols9-3 may be treated with methanesulfonyl chloride in the presence of abase such as triethylamine at temperatures from about −10° C. to about40° C. to provide sulfonates 9-4, wherein Ar¹ is as previously disclosed(Scheme 9, step c). Sulfonates 9-4 may be treated withHO—Ar²—C(O)O(C₁-C₄)alkyl, wherein Ar² is as previously disclosed, in thepresence of a base such as potassium carbonate, in a polar aproticsolvent, such as acetonitrile, at temperatures from about 50° C. toabout 90° C., to form esters 9-5, wherein Ar¹ and Ar² are as previouslydisclosed (Scheme 9, step d). Esters 9-5 may be treated with a metalhydroxide such as potassium hydroxide, sodium hydroxide, or lithiumhydroxide, in a solvent such as tetrahydrofuran, methanol, water, ormixtures thereof, to form carboxylic acids 9-6 (Scheme 9, step e).

Preparation of 2-Imino-1,3-Chalcogenazoheterocycles

Methods for preparation of the 2-imino-1,3-chalcogenazoheterocyclesrequired for preparation of molecules of Formula One are described inScheme 10. Anilines 10-1, wherein L² is as previously disclosed, may betreated with chloroacetyl chloride in the presence of a base, such assodium bicarbonate, in a polar aprotic solvent, such as ethyl acetate,at temperatures from about −10° C. to about 30° C., to form amides 10-2,wherein L² is as previously disclosed (Scheme 10, step a). Treatment ofamides 10-2 with potassium thiocyanate, in the presence of a base, suchas cesium carbonate, in a polar solvent, such as acetone, attemperatures from about 50° C. to about 75° C., to form2-imino-1,3-chalcogenazoheterocycles 10-3, wherein L² is as previouslydisclosed (Scheme 10, step b).

EXAMPLES

These examples are for illustration purposes and are not to be construedas limiting this disclosure to only the embodiments disclosed in theseexamples.

Starting materials, reagents, and solvents that were obtained fromcommercial sources were used without further purification. Anhydroussolvents were purchased as Sure/Seal™ from Aldrich and were used asreceived. Melting points were obtained on a Thomas Hoover Unimeltcapillary melting point apparatus or an OptiMelt Automated Melting PointSystem from Stanford Research Systems and are uncorrected. Examplesusing “room temperature” were conducted in climate controlledlaboratories with temperatures ranging from about 20° C. to about 24° C.Molecules are given their known names, named according to namingprograms within ISIS Draw, ChemDraw, or ACD Name Pro. If such programsare unable to name a molecule, such molecule is named using conventionalnaming rules. ¹H NMR spectral data are in ppm (δ) and were recorded at300, 400, 500, or 600 MHz; ¹³C NMR spectral data are in ppm (δ) and wererecorded at 75, 100, or 150 MHz, and ¹⁹F NMR spectral data are in ppm(δ) and were recorded at 376 MHz, unless otherwise stated.

Example 1 Preparation of1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-ol (C1)

A mixture of (4-(trifluoromethoxy)phenyl)hydrazine hydrochloride (2.00g, 8.75 mmol), urea (0.709 g, 11.81 mmol), and para-toluenesulfonic acidmonohydrate (0.0170 g, 0.0870 mmol) in chlorobenzene (7.95 mL) washeated at 140° C. for 2 hours. The mixture was cooled to 80° C., andtriethoxymethane (1.56 mL, 9.36 mmol) was added followed bychlorosulfonic acid (0.0120 mL, 0.175 mmol). The reaction mixture washeated at 80° C. for 4 hours. The reaction mixture was cooled to roomtemperature and filtered. The residue was dried under high vacuumovernight to provide the title compound (2.14 g, 99%): mp>300° C.; ¹HNMR (400 MHz, DMSO-d₆) δ 8.94 (s, 1H), 7.91-7.79 (m, 2H), 7.54 (dq,J=7.7, 1.0 Hz, 2H), 5.40 (s, 1H); ESIMS m/z 246 ([M+H]⁺).

Example 2 Preparation of methyl4-((((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoate(C2)

To a reaction vial were added1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-ol (C1) (0.500 g, 2.04mmol), potassium carbonate (0.423 g, 3.06 mmol), and acetonitrile (6.8mL). The reaction mixture was heated to 65° C. for 30 minutes.Tetrabutylammonium iodide (0.0226 g, 0.0610 mmol) and methyl4-(bromomethyl)benzoate (0.467 g, 2.04 mmol) were added, and thereaction mixture was stirred at 70-75° C. for 6 hours. The reactionmixture was cooled to room temperature and concentrated. The cruderesidue was treated with water, and extracted with dichloromethane. Theorganic layers were combined, dried over anhydrous sodium sulfate,filtered, and concentrated. Purification by flash chromatography usingethyl acetate/hexanes as eluent provided the title compound as a whitesolid (0.353 g, 44%): mp 123-125° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.26 (s,1H), 8.13-8.01 (m, 2H), 7.72-7.61 (m, 2H), 7.61-7.52 (m, 2H), 7.39-7.30(m, 2H), 5.47 (s, 2H), 3.92 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) 0-58.07;¹³C NMR (126 MHz, CDCl₃) δ 168.93, 166.79, 148.08, 148.06, 141.11,140.09, 135.41, 129.92, 129.80, 127.40, 122.38, 121.40, 120.46, 119.34,70.76, 52.16; ESIMS m/z 394 ([M+H]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 2:

Methyl3-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoate(C3)

Prepared from 1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-ol (C1)and isolated as an off-white solid (38%): ESIMS m/z 412 ([M+H]⁺).

Methyl3-methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoate(C4)

Prepared from 1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-ol (C1)and isolated as an off-white solid (38%): ESIMS m/z 424 ([M+H]⁺).

Methyl2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoate(C5)

Prepared from 1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-ol (C1)and isolated as an off-white solid (42%): ESIMS m/z 412 ([M+H]⁺).

Methyl5-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)picolinate(C6)

Prepared from 1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-ol (C1)and isolated as an off-white solid (65%): ESIMS m/z 395 ([M+H]⁺).

Example 3 Preparation of4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C7)

Methyl4-((((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoate(C2) (0.311 g, 0.791 mmol) and lithium hydroxide (0.178 g, 2.37 mmol)was dissolved in tetrahydrofuran (2.11 mL), methanol (2.11 mL), andwater (1.06 mL). The reaction mixture was stirred at room temperatureovernight. The reaction mixture was concentrated, diluted with water,and acidified with hydrochloric acid (2 N). The precipitate was filteredand dried in a vacuum oven providing the title compound as a white solid(0.300 g, 99%): mp 188-190° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 13.00 (s,1H), 9.10 (s, 1H), 7.99-7.95 (m, 2H), 7.95-7.88 (m, 2H), 7.63-7.54 (m,4H), 5.46 (s, 2H); ¹⁹F NMR (376 MHz, DMSO-d₆) δ −57.00; ¹³C NMR (126MHz, DMSO-d₆) δ 168.76, 167.49, 147.19, 142.88, 141.63, 136.08, 130.93,129.92, 128.20, 123.02, 121.52, 120.79, 70.63; ESIMS m/z 380 ([M+H]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 3:

4-((1-(4-(Trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C8)

Prepared from methyl4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C31) and isolated as a white solid (0.0520 g, 72%): mp 178-205° C.; ¹HNMR (400 MHz, DMSO-d₆) δ 12.69 (s, 1H), 9.36 (s, 1H), 8.07-7.95 (m, 2H),7.95-7.82 (m, 2H), 7.66-7.53 (m, 2H), 7.19-7.09 (m, 2H), 5.30 (s, 2H);¹⁹F NMR (376 MHz, DMSO-d₆) δ −56.97; ESIMS m/z 380 ([M+H]⁺).

2-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C9)

Prepared from methyl2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C32) and isolated as an off-white solid (0.165 g, 87%): mp 153-170° C.;¹H NMR (300 MHz, CDCl₃) δ 8.57 (s, 1H), 7.98 (t, J=8.7 Hz, 1H),7.81-7.65 (m, 2H), 7.39 (d, J=8.7 Hz, 2H), 7.05-6.74 (m, 2H), 5.30 (s,2H), 1.82 (s, 1H); ¹⁹F NMR (471 MHz, CDCl3) δ −58.03, −104.84; ESIMS m/z398 ([M+H]⁺).

2,6-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C10)

Prepared from methyl2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C33) and isolated as an off-white solid (0.250 g, 74%): mp 96-150° C.;¹H NMR (300 MHz, CDCl₃) δ 8.57 (s, 1H), 7.98 (t, J=8.7 Hz, 1H),7.81-7.65 (m, 2H), 7.39 (d, J=8.7 Hz, 2H), 7.05-6.74 (m, 2H), 5.30 (s,2H), 1.82 (s, 1H); ¹⁹F NMR (471 MHz, CDCl3) δ −58.03, −104.84; ESIMS m/z416 ([M+H]⁺).

2-Methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C11)

Prepared from methyl2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C34) and isolated as an off-white solid (0.6 g, 95%): mp 182-184° C.,¹H NMR (400 MHz, DMSO-d₆) δ 12.47 (br s, 1H), 9.35 (s, 1H), 8.05-7.94(m, 2H), 7.84 (d, J=8.3 Hz, 1H), 7.60 (d, J=8.3 Hz, 2H), 7.05-6.91 (m,2H), 5.27 (s, 2H), 2.91 (s, 3H); ¹⁹F NMR (376 MHz, DMSO-d₆) δ −57.00;ESIMS m/z 394 ([M+H]⁺).

2-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C12)

Prepared from methyl2-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C35) and isolated as an off-white solid (0.45 g, 84%): mp 199-201° C.;¹H NMR (400 MHz, DMSO-d₆) δ 12.64 (s, 1H), 9.35 (s, 1H), 8.04-7.95 (m,2H), 7.78 (d, J=8.8 Hz, 1H), 7.60 (d, J=8.8 Hz, 1H), 7.24 (d, J=2.0 Hz,1H), 7.08 (dd, J=2.4, 8.8 Hz, 1H), 5.31 (s, 2H); ¹⁹F NMR (376 MHz,DMSO-d₆) δ −56.99; ESIMS m/z 414 ([M+H]⁺).

2-Methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C13)

Prepared from methyl2-methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C36) and isolated as an off-white solid (1.3 g, 96%): mp 153-155° C.;¹H NMR (400 MHz, DMSO-d₆) δ 12.64 (s, 1H), 9.35 (s, 1H), 8.04-7.95 (m,3H), 7.62-7.56 (m, 1H), 6.65 (d, J=2.4 Hz, 1H), 5.26 (s, 2H), 3.78 (s,3H); ¹⁹F NMR (376 MHz, DMSO-d₆) δ −56.99; ESIMS m/z 410 ([M+H]⁺).

3-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C14)

Prepared from methyl3-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C37) and isolated as an off-white solid (1.1 g, 88%): mp 201-203° C.;¹H NMR (300 MHz, DMSO-d₆) δ 9.36 (s, 1H), 8.06-7.84 (m, 3H), 7.93-7.82(m, 1H), 7.60 (d, J=8.4 Hz, 2H), 7.52-7.36 (m, 2H), 5.41 (s, 2H); ¹⁹FNMR (282 MHz, DMSO-d₆) δ −56.95; ESIMS m/z 414 ([M+H]⁺).

3-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C15)

Prepared from methyl3-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C38) and isolated as an off-white solid (2 g, 94%): mp 192-194° C.; ¹HNMR (300 MHz, DMSO-d₆) δ 13.0 (s, 1H), 9.36 (s, 1H), 8.02-7.97 (m, 2H),7.77 (d, J=9.3 Hz, 1H), 7.69 (dd, J=2.0, 13.0 Hz, 1H), 7.60 (d, J=9.3Hz, 2H), 7.48 (t, J=9.6 Hz, 1H), 5.40 (s, 2H); ¹⁹F NMR (376 MHz,DMSO-d₆) δ −56.96, −133.90; ESIMS m/z 398 ([M+H]⁺).

3,5-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C16)

Prepared from methyl3,5-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C39) and isolated as an off-white solid (1.4 g, 90%): mp 223-225° C.;¹H NMR (300 MHz, DMSO-d₆) δ 9.32 (s, 1H), 7.96 (dd, J=2.1, 9.2 Hz, 2H),7.59 (d, J=9.2 Hz, 2H), 7.49 (d, J=12.0 Hz, 2H), 5.28 (s, 2H); ¹⁹F NMR(282 MHz, DMSO-d₆) δ −56.96, −127.84; ESIMS m/z 416 ([M+H]⁺).

5-((1-(4-(Trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)picolinicacid (C17)

Prepared from methyl5-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)picolinate(C40) and isolated as an off-white solid (1.6 g, 98%): mp 253-255° C.;¹H NMR (400 MHz, DMSO-d₆) δ 12.89 (br s, 1H), 9.36 (s, 1H), 8.41 (d,J=2.4 Hz, 1H), 8.04-7.94 (m, 3H), 7.67-7.55 (m, 3H), 5.39 (s, 2H); ¹⁹FNMR (376 MHz, DMSO-d₆) δ −57.00; ESIMS m/z 381 ([M+H]⁺).

6-((1-(4-(Trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)nicotinicacid (C18)

Prepared from methyl6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)nicotinate(C41) and isolated as an off-white solid (1 g, 98%): mp 233-235° C.; ¹HNMR (400 MHz, DMSO-d₆) δ 12.89 (br s, 1H), 9.26 (s, 1H), 8.62 (d, J=2.4Hz, 1H), 7.97-7.88 (m, 2H), 7.83 (dd, J=2.4, 9.8 Hz, 1H), 7.57 (d, J=8.3Hz, 2H), 6.45 (d, J=9.3 Hz, 1H), 5.36 (s, 2H); ¹⁹F NMR (376 MHz,DMSO-d₆) δ −57.01; ESIMS m/z 381 ([M+H]⁺).

2-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C19)

Prepared from methyl2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl) benzoate (C5) and isolated as an off-white solid (0.621 g, 83%):mp 212-213° C.; ¹H NMR (300 MHz, DMSO-d₆) δ 13.20 (br s, 1H), 9.10 (s,¹H), 7.93-7.87 (m, 3H), 7.57 (d, J=8.4 Hz, 2H), 7.41 (d, J=9.9 Hz, 2H),5.45 (s, 2H); ¹⁹F NMR (282.2 MHz, DMSO-d₆) δ −56.99, −110.40; ESIMS m/z398 ([M+H]⁺).

5-(((1-(4-(Trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)picolinicacid (C20)

Prepared from methyl5-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)picolinate(C6) and isolated as an off-white solid (0.530 g, 84%): mp 195-197° C.;¹H NMR (300 MHz, DMSO-d₆) δ 13.25 (br s, 1H), 9.10 (s, 1H), 8.82 (s,¹H), 8.08 (s, 2H), 7.92 (d, J=8.7 Hz, 2H), 7.57 (d, J=9.0 Hz, 2H), 5.51(s, 2H); ¹⁹F (282.2 MHz, DMSO-d₆) δ −56.99; ESIMS m/z 381 ([M+H]⁺).

3-Methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C21)

Prepared from methyl3-methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl) benzoate (C4) and isolated as an off-white solid (95%): mp214-216° C.; ¹H NMR (300 MHz, DMSO-d₆) δ 13.10 (br s, 1H), 9.09 (s, 1H),7.94-7.90 (m, 2H), 7.61-7.55 (m, 5H), 5.41 (s, 2H), 3.90 (s, 3H); ¹⁹F(282.2 MHz, DMSO-d₆) δ−56.99; ESIMS m/z 410 ([M+H]⁺).

3-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C22)

Prepared from methyl3-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoate(C3) and isolated as an off-white solid (95%): mp 258-260° C.; ¹H NMR(300 MHz, DMSO-d₆) δ 13.25 (br s, 1H), 9.10 (s, 1H), 7.92 (d, J=9.0 Hz,2H), 7.81 (d, J=6.6 Hz, 1H), 7.75-7.70 (m, 2H), 7.57 (d, J=8.7 Hz, 2H),5.49 (s, 2H); ¹⁹F (282.2 MHz, DMSO-d₆) δ −56.98, −117.29; ESIMS m/z 398([M+H]⁺).

Example 4 Preparation of4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoylazide (C23)

To4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C7) (0.230 g, 0.606 mmol) in toluene (3.03 mL) was addedtriethylamine (0.110 mL, 0.789 mmol). The reaction mixture was stirred 5minutes after which time, diphenylphosphoryl azide (0.131 mL, 0.606mmol) was added. The reaction mixture was stirred at room temperature.After 1.5 hours, the reaction mixture was diluted with ethyl acetate andwashed with water. The water was extracted an additional time with ethylacetate. The organic layers were dried over anhydrous sodium sulfate,filtered, and concentrated. Purification by flash column chromatographyusing 0-100% ethyl acetate/hexanes as eluent provided the title compound(0.185 g, 75%): ¹H NMR (400 MHz, CDCl₃) δ 8.26 (s, 1H), 8.11-8.01 (m,2H), 7.70-7.62 (m, 2H), 7.62-7.52 (m, 2H), 7.34 (dq, J=8.6, 0.8 Hz, 2H),5.48 (s, 2H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.07; ESIMS m/z 405 ([M+H]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 4:

4-((1-(4-(Trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoylazide (C24)

Prepared from4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C8) (0.040 g, 72%): ¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H),8.06-7.95 (m, 2H), 7.78-7.66 (m, 2H), 7.38 (dt, J=7.9, 1.0 Hz, 2H),7.15-7.06 (m, 2H), 5.31 (s, 2H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.03;ESIMS m/z 405 ([M+H]⁺).

2-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoylazide (C25)

Prepared from2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C9) and isolated as an off-white solid (0.111 g, 63%): ¹H NMR (300MHz, CDCl₃) δ 8.55 (s, 1H), 7.99-7.83 (m, 1H), 7.81-7.62 (m, 2H),7.47-7.30 (m, 2H), 6.99-6.78 (m, 2H), 5.30 (s, 2H); ¹³C NMR (126 MHz,CDCl₃) δ 160.90, 141.89, 141.81, 135.15, 133.38, 132.67, 125.34, 122.44,121.50, 121.48, 111.00, 103.77, 103.53, 99.99, 63.75.

2,6-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoylazide (C26)

Prepared from2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C10) and isolated as a white solid (0.107 g, 40%): ¹H NMR (300MHz, CDCl₃) δ 8.63-8.44 (m, 1H), 7.80-7.64 (m, 2H), 7.45-7.29 (m, 2H),6.78-6.57 (m, 1H), 5.17 (d, J=23.3 Hz, 1H), 4.64 (s, 1H), 3.52 (s, 1H).

2-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoylazide (C27)

Prepared from2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C19) and isolated as a white solid (0.107 g, 40%): ¹H NMR (300MHz, CDCl₃) δ 8.55 (s, 1H), 8.02-7.81 (m, 1H), 7.81-7.65 (m, 2H), 7.38(ddd, J=7.8, 2.0, 1.0 Hz, 2H), 6.97-6.76 (m, 2H), 5.30 (s, 2H); ¹³C NMR(126 MHz, CDCl₃) δ 160.90, 141.89, 141.81, 135.15, 133.38, 132.67,125.34, 122.44, 121.50, 121.48, 111.00, 103.77, 103.53, 99.99, 63.75;¹⁹F NMR (376 MHz, CDCl₃) δ −58.07, −108.00.

Example 5 Preparation of(Z)-1-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F1)

4-(((1-(4-(Trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoylazide (C23) (0.0900 g, 0.223 mmol) in acetonitrile (1.1 mL) was heatedat 80° C. for 2 hours. The reaction mixture was cooled to roomtemperature, and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-one(0.0553 g, 0.223 mmol) was added. The reaction mixture was stirred atroom temperature until determined complete. The reaction mixture wasdiluted with ethyl acetate and loaded onto silica gel. Purification byflash column chromatography using 0-100% ethyl acetate/hexanes as eluentprovided the title compound as an off-white solid (0.0870 g, 62%).

The following compounds were prepared in like manner to the procedureoutlined in Example 5:

(Z)-1-(3-(4-Fluoro-2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F12)

Prepared from2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoylazide (C27) and3-(4-fluoro-2-isopropyl-5-methylphenyl)-2-iminothiazolidin-4-one (C54)and isolated as a white solid (0.030 g, 38%).

(Z)-1-(3-(2-Isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F15)

Prepared from4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoylazide (C24) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.046 g, 74%).

(Z)-1-(2-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(1-methoxyethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F20)

Prepared from2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoylazide (C25) and2-imino-3-(2-(1-methoxyethyl)-5-methylphenyl)thiazolidin-4-one (C51) andisolated as an off-white solid (0.042 g, 61%).

(Z)-1-(2,6-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(1-methoxyethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F21)

Prepared from2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoylazide (C26) and2-imino-3-(2-(1-methoxyethyl)-5-methylphenyl)thiazolidin-4-one (C51) andisolated as an off-white solid (0.012 g, 25%).

Example 6 Preparation of(Z)-1-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F1)

Step 1. Preparation of4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoylazide (C23)

To a stirred solution of4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C7) (0.200 g, 0.536 mmol) in toluene (5 mL) were addeddiphenylphosphoryl azide (0.150 g, 0.536 mmol), triethylamine (0.0700 g,0.693 mmol) at 0° C. The reaction mixture was stirred at roomtemperature for 4 hours. The reaction mixture was concentrated, and theresidue was diluted with water. The resultant solid was filtered anddried to obtain the title compound as an off-white solid (0.180 g, 85%).The crude compound was directly used in the next step without furtherpurification.

Step 2. Preparation of(Z)-1-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F1)

A single-necked round-bottomed flask (25 mL) was charged with4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoylazide (C23) (0.180 g, 0.502 mmol) which was dissolved in acetonitrile (5mL). The reaction mixture was heated to 70° C. for 2 hours, and thencooled to room temperature.2-Imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-one (0.190 g, 0.754mmol) was added, and the reaction mixture was stirred at roomtemperature for 16 hours. The reaction mixture was concentrated, and theresulting residue was purified by preparative HPLC to provide the titlecompound as an off-white solid (0.120 g, 37%).

The following compounds were prepared in like manner to the procedureoutlined in Example 6:

(Z)-1-(2-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F2)

Prepared from2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C19) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.033 g, 14%).

(Z)-1-(3-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F3)

Prepared from3-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C22) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.033 g, 18%).

(Z)-1-(3-(2-Isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(3-methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F4)

Prepared from3-methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C21) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.122 g, 18%).

(Z)-1-(3-(5-Methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F5)

Prepared from4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C7) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one (C53)and isolated as an off-white solid (0.045 g, 10%).

(Z)-1-(2-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F6)

Prepared from2-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C19) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as an off-white solid (0.030 g, 18%).

(Z)-1-(3-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F7)

Prepared from3-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C22) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as an off-white solid (0.080 g, 20%).

(Z)-1-(3-(2-(Methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)urea(F8)

Prepared from4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C7) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.090 g, 20%).

(Z)-1-(3-Fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F9)

Prepared from3-fluoro-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C22) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.055 g, 15%).

(Z)-1-(3-Methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F10)

Prepared from3-methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C21) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as an off-white solid (0.025 g, 6%).

(Z)-1-(3-Methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F11)

Prepared from3-methoxy-4-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)benzoicacid (C21) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.025 g, 10%).

(Z)-1-(3-(5-Methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)-3-(5-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)pyridin-2-yl)urea(F13)

Prepared from5-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)picolinicacid (C20) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as an off-white solid (0.060 g, 20%).

(Z)-1-(3-(2-Isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(5-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)pyridin-2-yl)urea(F14)

Prepared from5-(((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)oxy)methyl)picolinicacid (C20) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.040 g, 15%).

(Z)-1-(2-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F16)

Prepared from2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C9) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.140 g, 63%).

(Z)-1-(3-(5-Methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F17)

Prepared from4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C8) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one (C53)and isolated as a pale-yellow solid (0.1 g, 43%).

-   -   (Z)-1-(2,6-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea        (F18)

Prepared from2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C10) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.030 g, 20%).

(Z)-1-(2,6-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F19)

Prepared from2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C10) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as a pale-yellow solid (0.030 g, 20%).

(Z)-1-(3-(2-(Methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F22)

Prepared from4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C8) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.025 g, 11%).

(Z)-1-(2-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F23)

Prepared from2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C9) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one (C53)and isolated as a pale-yellow solid (0.140 g, 62%).

(Z)-1-(2-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F24)

Prepared from2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C9) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.035 g, 16%).

(Z)-1-(3-(2-Isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F25)

Prepared from2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C11) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.055 g, 45%).

(Z)-1-(3-(5-Methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)-3-(2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F26)

Prepared from2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C11) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a pale-yellow solid (0.045 g, 36%).

(Z)-1-(3-(2-(Methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F27)

Prepared from2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C11) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.040 g, 37%).

(Z)-1-(2,6-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F28)

Prepared from2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C10) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a pale-yellow solid (0.015 g, 10%).

(Z)-1-(2-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F29)

Prepared from2-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C12) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.070 g, 46%).

(Z)-1-(2-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F30)

Prepared from2-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C12) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as an off-white solid (0.040 g, 26%).

(Z)-1-(2-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F31)

Prepared from2-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C12) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.025 g, 13%).

(Z)-1-(3-(2-Isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(2-methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)urea(F32)

Prepared from2-methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C13) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.030 g, 13%).

(Z)-1-(2-Methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F33)

Prepared from2-methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C13) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a brown solid (0.065 g, 28%).

(Z)-1-(2-Methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F34)

Prepared from2-methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C13) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.090 g, 39%).

(Z)-1-(3-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F35)

Prepared from3-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C15) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as a pale-yellow solid (0.070 g, 38%).

(Z)-1-(3-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F36)

Prepared from3-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C15) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a brown solid (0.100 g, 54%).

(Z)-1-(3-Fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F37)

Prepared from3-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C15) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.100 g, 43%).

(Z)-1-(3-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F38)

Prepared from3-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C14) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.100 g, 66%).

(Z)-1-(3-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F39)

Prepared from3-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C14) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a pale-yellow solid (0.040 g, 26%).

(Z)-1-(3-Chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F40)

Prepared from3-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C14) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.150 g, 57%).

(Z)-1-(3,5-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F41)

Prepared from3,5-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C16) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as an off-white solid (0.100 g, 44%).

(Z)-1-(3,5-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(5-methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)urea(F42)

Prepared from3,5-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C16) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a pale-yellow solid (0.055 g, 24%).

(Z)-1-(3,5-Difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)phenyl)-3-(3-(2-(methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)urea(F43)

Prepared from3,5-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoicacid (C16) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.080 g, 31%).

(Z)-1-(3-(2-Isopropyl-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)pyridin-3-yl)urea(F44)

Prepared from6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)nicotinicacid (C18) and 2-imino-3-(2-isopropyl-5-methylphenyl)thiazolidin-4-oneand isolated as a brown solid (0.065 g, 21%).

(Z)-1-(3-(5-Methyl-2-propylphenyl)-4-oxothiazolidin-2-ylidene)-3-(6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)pyridin-3-yl)urea

(F45)

Prepared from6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)nicotinicacid (C18) and 2-imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one(C53) and isolated as a brown solid (0.090 g, 29%).

(Z)-1-(3-(2-(Methoxymethyl)-5-methylphenyl)-4-oxothiazolidin-2-ylidene)-3-(6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)pyridin-3-yl)urea(F46)

Prepared from6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)nicotinicacid (C18) and2-imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52) andisolated as an off-white solid (0.075 g, 24%).

Example 7 Preparation of methyl1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole-3-carboxylate (C28)

To a reaction flask was added methyl 1H-1,2,4-triazole-3-carboxylate(5.00 g, 39.3 mmol), (4-(trifluoromethoxy)phenyl)boronic acid (8.10 g,39.3 mmol), and copper(II) acetate (7.15 g, 39.3 mmol). The flask wassealed, and evacuated/backfilled with nitrogen (3×). Dichloromethane(157 mL) was added, followed by pyridine (4.77 mL, 59.0 mmol). Thereaction mixture was allowed to stir at room temperature overnight.Water was added, and the reaction mixture was filtered through Celite®.The filtrate was transferred to a separatory funnel, and the layers wereseparated. The organic layers were further washed with water (3×),combined, dried over sodium sulfate, filtered, and concentrated. Thecrude product was triturated with a small amount of ethylacetate/hexanes and filtered to provide the title compound as a whitesolid (2.17 g, 19%): mp 156-158° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.65 (s,1H), 7.86-7.75 (m, 2H), 7.48-7.32 (m, 2H), 4.06 (s, 3H); ¹⁹F NMR (471MHz, CDCl₃) δ −58.00; ¹³C NMR (126 MHz, CDCl₃) δ 159.89, 149.29, 134.81,122.44, 122.07, 121.35, 119.29, 53.06; EIMS m/z 288 ([M]⁺).

Example 8 Preparation of(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methanol (C29)

To a reaction flask was added methyl1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole-3-carboxylate (C28)(0.500 g, 1.74 mmol). The flask was sealed and evacuated/backfilled withnitrogen (3×). Tetrahydrofuran (14.5 mL) was added, and the flask wascooled to 0° C. Lithium aluminum hydride (1 M, 1.74 mL, 1.74 mmol) wasadded dropwise. The reaction mixture was allowed to warm to roomtemperature. The reaction mixture was cooled to 0° C., diluted withethyl acetate, and quenched with water. The mixture was filtered throughCelite®, and the Celite® was washed with ethyl acetate. Purification byflash column chromatography using ethyl acetate/hexanes as eluentprovided the title compound as a white solid (0.233 g, 51%): mp 147-149°C.; ¹H NMR (400 MHz, CDCl₃) δ 8.51 (s, 1H), 7.79-7.64 (m, 2H), 7.37 (dq,J=8.9, 0.9 Hz, 2H), 4.86 (d, J=6.2 Hz, 2H), 2.41 (t, J=6.2 Hz, 1H); ¹⁹FNMR (376 MHz, CDCl₃) δ −58.03.

Example 9 Preparation of(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30)

To a reaction vial was added(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methanol (C29)(0.100 g, 0.386 mmol). The flask was sealed and evacuated/backfilledwith nitrogen (3×). Dichloromethane (3.9 mL) was added, and the flaskwas cooled to 0° C. Triethylamine (0.0970 mL, 0.694 mmol) was added,followed by methanesulfonyl chloride (0.0540 mL, 0.694 mmol) dropwise.The reaction mixture was stirred at 0° C. for 30 minutes and allowed towarm to room temperature. The reaction mixture was diluted withdichloromethane and washed with cold water. The organics were dried oversodium sulfate, filtered, and concentrated providing the title compoundwhich was used without further purification (0.130 g, 99%): ¹H NMR (400MHz, CDCl₃) δ 8.54 (d, J=14.4 Hz, 1H), 7.79-7.65 (m, 2H), 7.45-7.31 (m,2H), 5.41 (s, 2H), 3.16 (s, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −58.03; ¹³CNMR (126 MHz, CDCl₃) δ 159.14, 142.07, 135.00, 122.47, 121.51, 121.45,63.73, 45.92, 38.53, 8.62.

Example 10 Preparation of methyl4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C31)

To a reaction vial was added methyl 4-hydroxybenzoate (0.0586 g, 0.385mmol), potassium carbonate (0.0800 g, 0.578 mmol), and acetonitrile (1.3mL). The reaction mixture was heated to 65° C. for 30 minutes afterwhich time, (1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) (0.130 g, 0.385 mmol) was added. The reactionmixture was stirred at 70-75° C. for 1.5 hours. The reaction mixture wascooled to room temperature and concentrated. The crude residue wastreated with water and extracted with dichloromethane. The organiclayers were combined, dried over anhydrous sodium sulfate, filtered, andconcentrated. Purification by flash column chromatography using ethylacetate/hexanes as eluent provided the title compound as an off-whitesolid (0.0750 g, 50%): mp 101-103° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.55(s, 1H), 8.08-7.93 (m, 2H), 7.77-7.66 (m, 2H), 7.38 (dq, J=8.8, 0.9 Hz,2H), 7.14-7.04 (m, 2H), 5.30 (s, 2H), 3.89 (s, 3H); ¹⁹F NMR (376 MHz,CDCl₃) δ −58.03; ESIMS m/z 394 ([M+H]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 10:

Methyl2-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C32)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (0.290 g,82%): ¹H NMR (400 MHz, CDCl₃) δ 8.55 (s, 1H), 8.08-7.93 (m, 2H),7.77-7.66 (m, 2H), 7.38 (dq, J=8.8, 0.9 Hz, 2H), 7.14-7.04 (m, 2H), 5.30(s, 2H), 3.89 (s, 3H); ¹⁹F NMR (471 MHz, CDCl₃) δ −58.03, −105.87; ¹³CNMR (126 MHz, CDCl₃) δ 164.63, 163.12, 162.25, 160.56, 141.85, 135.12,133.49, 122.44, 121.50, 121.06, 111.59, 110.84, 103.55, 103.34, 63.56,52.08; ESIMS m/z 412 ([M+H]⁺).

Methyl2,6-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C33)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as a white solid (2.0 g, 71%): mp147-149° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 7.72 (dd, J=2.3,7.6 Hz, 2H), 7.38 (d, J=9.3 Hz, 2H), 6.67 (dd, J=1.6, 12.6 Hz, 2H), 5.25(s, 2H), 3.91 (s, 3H); ¹⁹F NMR (282 MHz, CDCl₃) δ −58.02, −107.43; ESIMSm/z 430 ([M+H]⁺).

Methyl2-methyl-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C34)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (1.1 g, 91%):mp 106-107° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.53 (s, 1H), 8.08-7.93 (m,1H), 7.77-7.66 (m, 2H), 7.38 (dq, J=9.3 Hz, 2H), 6.92-6.89 (m, 2H), 5.27(s, 2H), 3.85 (s, 3H), 2.60 (s, 3H); ¹⁹F NMR (282 MHz, CDCl₃) δ −58.02;ESIMS m/z 408 ([M+H]⁺).

Methyl2-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C35)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (0.9 g, 71%):mp 101-102° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 7.88 (d, J=10.0Hz, 1H), 7.72 (dd, J=2.3, 7.6 Hz, 2H), 7.37 (d, J=9.6 Hz, 2H), 7.17 (d,J=2.6 Hz, 1H), 6.99 (dd, J=3.0, 9.6 Hz, 1H), 5.27 (s, 2H), 3.89 (s, 3H);¹⁹F NMR (282 MHz, CDCl₃) δ −58.02; ESIMS m/z 428 ([M+H]⁺).

Methyl2-methoxy-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C36)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (1.7 g, 68%):mp 140-142° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.54 (s, 1H), 7.85 (d, J=5.2Hz, 1H), 7.72 (dd, J=1.0, 4.4 Hz, 2H), 7.37 (d, J=5.2 Hz, 2H), 6.69-6.65(m, 2H), 5.29 (s, 2H), 3.88 (s, 3H), 3.85 (s, 3H); ¹⁹F NMR (376 MHz,CDCl₃) δ −58.07; ESIMS m/z 424 ([M+H]⁺).

Methyl3-chloro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C37)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (1.7 g, 47%):mp 115-117° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 8.07 (d, J=2.0Hz, 1H), 7.93 (dd, J=2.3, 9.3 Hz, 1H), 7.72 (dd, J=2.0, 7.3 Hz, 2H),7.37 (d, J=10.0 Hz, 2H), 7.22 (d, J=9.66 Hz, 1H), 5.38 (s, 2H), 3.89 (s,3H); ¹⁹F NMR (282 MHz, CDCl₃) δ −58.02; ESIMS m/z 428 ([M+H]⁺).

Methyl3-fluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C38)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (2.5 g, 92%):mp 90-92° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.54 (s, 1H), 7.83-7.70 (m, 4H),7.37 (d, J=10.0 Hz, 1H), 7.21 (d, J=9.3 Hz, 1H), 5.36 (s, 2H), 3.89 (s,3H); ¹⁹F NMR (282 MHz, CDCl₃) δ −58.02, −132.60; ESIMS m/z 412 ([M+H]⁺).

Methyl3,5-difluoro-4-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)benzoate(C39)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (2.1 g, 75%):mp 98-100° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.51 (s, 1H), 7.70 (d, J=10.3Hz, 2H), 7.60 (d, J=9.6 Hz, 2H), 7.36 (d, J=9.3 Hz, 2H), 5.43 (s, 2H),3.90 (s, 3H); ¹⁹F NMR (282 MHz, CDCl₃) δ −58.03, −125.83; ESIMS m/z 430([M+H]⁺).

Methyl5-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)picolinate(C40)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (2.3 g, 76%):mp 138-140° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.55 (d, J=3.6 Hz, 2H), 8.13(d, J=10.0 Hz, 1H), 7.71 (dd, J=2.6, 8.0 Hz, 2H), 7.49 (dd, J=3.3, 10.0Hz, 1H), 7.38 (d, J=9.6 Hz, 2H), 5.36 (s, 2H), 3.98 (s, 3H); ¹⁹F NMR(282 MHz, CDCl₃) δ −58.03; ESIMS m/z 395 ([M+H]+).

Methyl6-((1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methoxy)nicotinate(C41)

Prepared from(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)methylmethanesulfonate (C30) and isolated as an off-white solid (2.5 g, 83%):mp 133-135° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.48 (s, 1H), 8.38 (d, J=3.0Hz, 1H), 7.87 (dd, J=2.6, 10.6 Hz, 1H), 7.68 (dd, J=2.6, 8.0 Hz, 2H),7.35 (d, J=9.3 Hz, 2H), 6.59 (d, J=10.6 Hz, 1H), 5.35 (s, 2H), 3.85 (s,3H); ¹⁹F NMR (282 MHz, CDCl₃) δ −58.04; ESIMS m/z 395 ([M+H]⁺).

Example 11 Preparation of1-fluoro-2-methyl-4-nitro-5-(prop-1-en-2-yl)benzene (C42)

To a reaction vial were added 1-chloro-5-fluoro-4-methyl-2-nitrobenzene(1.50 g, 7.91 mmol),4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (1.79 mL,9.50 mmol), bis(triphenylphosphine)palladium(II) dichloride (0.444 g,0.633 mmol), and sodium carbonate (1.01 g, 9.50 mmol). Water (2.85 mL)and dioxane (11.4 mL) were added. The vial was capped and heated at 140°C. for 30 minutes in a Biotage Initiator® microwave reactor, withexternal IR-sensor temperature monitoring from the side of the vessel.The reaction mixture was cooled to room temperature, diluted with ethylacetate, and washed with water. The aqueous layer was further extractedwith ethyl acetate (3×). The combined organic layers were dried overmagnesium sulfate, filtered, and concentrated. Purification by flashcolumn chromatography eluting with 0-40% ethyl acetate/hexanes providedthe title compound as a yellow liquid (1.42 g, 88%): ¹H NMR (400 MHz,CDCl₃) δ 7.81 (dd, J=7.0, 0.9 Hz, 1H), 6.95 (d, J=9.4 Hz, 1H), 5.17 (t,J=1.5 Hz, 1H), 4.97-4.86 (m, 1H), 2.33 (dd, J=2.0, 0.8 Hz, 3H), 2.06(dd, J=1.6, 0.9 Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −108.66; EIMS m/z195 ([M]⁺).

Example 12 Preparation of 4-fluoro-2-isopropyl-5-methylaniline (C43)

To a reaction flask were added1-fluoro-2-methyl-4-nitro-5-(prop-1-en-2-yl)benzene (C42) (1.41 g, 7.22mmol) in ethyl acetate (29 mL) and palladium on carbon (10 weight %,0.770 g, 0.720 mmol). The flask was evacuated, then backfilled withhydrogen (balloon) (3×). The reaction mixture was stirred under hydrogenby balloon overnight. The reaction mixture was filtered through Celite®and concentrated to afford the title compound as a yellow liquid (1.10g, 90%): ¹H NMR (400 MHz, CDCl₃) δ 6.79 (d, J=11.1 Hz, 1H), 6.49 (d,J=7.0 Hz, 1H), 3.39 (s, 2H), 2.91-2.80 (m, 1H), 2.17 (d, J=2.0 Hz, 3H),1.22 (d, J=6.8 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ 138.55, 122.03,118.40, 118.35, 111.97, 111.73, 27.63, 22.29, 14.16; EIMS m/z 167([M]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 12:

2-(Methoxymethyl)-5-methylaniline (C44)

Prepared from 1-(methoxymethyl)-4-methyl-2-nitrobenzene (C59) andisolated as an orange oil (1.6 g, 100%): ¹H NMR (400 MHz, CDCl₃) δ 6.94(d, J=7.3 Hz, 1H), 6.56-6.49 (m, 2H), 4.44 (s, 2H), 4.11 (s, 2H), 3.32(s, 3H), 2.26 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 146.16, 139.28,130.09, 119.27, 118.70, 116.44, 73.46, 57.26, 21.25; EIMS m/z 151([M]+).

Example 13 Preparation of 2-chloro-N-(2-fluoro-5-methylphenyl)acetamide(C45)

To a reaction flask were added 2-fluoro-5-methylaniline (3.00 g, 24.0mmol) and ethyl acetate (24.0 mL). The reaction mixture was cooled to 0°C. Sodium bicarbonate (4.03 g, 47.9 mmol) was added, followed bydropwise addition of chloroacetyl chloride (2.30 mL, 28.8 mmol) over 4minutes. The reaction mixture was allowed to stir at 0° C. for 10minutes, then was allowed to warm to room temperature and was furtherstirred for 90 minutes. Water (15 mL) was added to the reaction mixture,and the phases were separated. The organic layers were washed with brine(20 mL), dried over magnesium sulfate, filtered, and concentrated toafford the title compound (4.83 g, 100%): ¹H NMR (400 MHz, CDCl₃) δ 8.47(s, 1H), 8.08 (dd, J=7.5, 2.1 Hz, 1H), 7.00 (dd, J=10.7, 8.4 Hz, 1H),6.90 (dddd, J=8.3, 5.0, 2.2, 0.8 Hz, 1H), 4.21 (s, 2H), 2.34 (d, J=0.9Hz, 3H); ¹⁹F NMR (376 MHz, CDCl₃) δ −135.59; ¹³C NMR (126 MHz, CDCl₃) δ163.83, 151.92, 150.00, 134.42, 125.79, 121.94, 114.64, 42.92, 21.08;ESIMS m/z 201 ([M+H]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 13:

2-Chloro-N-(2-(1-methoxyethyl)-5-methylphenyl)acetamide (C46)

Prepared from 2-(1-methoxyethyl)-5-methylaniline (C58) and isolated as ayellow oil (2.19 g, 71%): ¹H NMR (300 MHz, CDCl₃) δ 10.16 (s, 1H), 8.17(s, 1H), 7.02 (d, J=7.7 Hz, 1H), 6.99-6.85 (m, 1H), 4.45 (q, J=6.7 Hz,1H), 4.20 (dd, J=2.6, 1.1 Hz, 2H), 3.34 (d, J=1.1 Hz, 3H), 2.37 (d,J=1.0 Hz, 3H), 1.52 (dd, J=6.9, 1.0 Hz, 3H); ¹³C NMR (126 MHz, CDCl₃) δ164.22, 138.56, 135.55, 128.26, 127.41, 125.20, 122.16, 80.90, 77.31,77.05, 76.80, 56.25, 43.10, 21.37, 20.95.

2-Chloro-N-(2-(methoxymethyl)-5-methylphenyl)acetamide (C47)

Prepared from 2-(methoxymethyl)-5-methylaniline (C44) and isolated as anorange oil (1.89 g, 77%): ¹H NMR (400 MHz, CDCl₃) δ 9.74 (s, 1H),8.01-7.95 (m, 1H), 7.09 (d, J=7.6 Hz, 1H), 6.97-6.88 (m, 1H), 4.49 (s,2H), 4.23 (s, 2H), 3.43 (s, 3H), 2.36 (s, 3H); ¹³C NMR (101 MHz, CDCl₃)δ 164.65, 139.40, 136.56, 129.19, 125.42, 124.08, 122.41, 73.55, 58.01,43.06, 40.47; EIMS m/z 227 ([M]⁺).

2-Chloro-N-(5-methyl-2-propylphenyl)acetamide (C48)

Prepared from 5-methyl-2-propylaniline and isolated as a pink solid(1.86 g, 92%): mp 108-111° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.28 (s, 1H),7.74-7.69 (m, 1H), 7.09 (d, J=7.8 Hz, 1H), 6.98-6.94 (m, 1H), 4.24 (s,2H), 2.55 (dd, J=8.6, 6.8 Hz, 2H), 2.34 (s, 3H), 1.67-1.57 (m, 2H), 0.99(td, J=7.3, 2.9 Hz, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 132.21, 130.32,129.67, 126.64, 123.34, 43.24, 33.16, 23.23, 13.94; EIMS m/z 225 ([M]⁺).

2-Chloro-N-(4-fluoro-2-isopropyl-5-methylphenyl)acetamide (C49)

Prepared from 4-fluoro-2-isopropyl-5-methylaniline (C43) and isolated asan orange solid (1.20 g, 85%): mp 126-134° C.; ¹H NMR (400 MHz, CDCl₃) δ8.13 (s, 1H), 7.50 (d, J=7.4 Hz, 1H), 6.94 (d, J=10.9 Hz, 1H), 4.24 (s,2H), 3.05-2.88 (m, 1H), 2.24 (dd, J=2.0, 0.7 Hz, 3H), 1.24 (d, J=6.8 Hz,6H); ¹⁹F NMR (376 MHz, CDCl₃) δ −118.99; EIMS m/z 243 ([M]⁺).

Example 14 Preparation of3-(2-fluoro-5-methylphenyl)-2-iminothiazolidin-4-one (C50)

To a reaction flask were added2-chloro-N-(2-fluoro-5-methylphenyl)acetamide (C45) (2.00 g, 9.92 mmol)and acetone (9.92 mL). Potassium thiocyanate (1.93 g, 19.8 mmol) wasadded as a solid, and the reaction mixture was heated at 65° C. for 3hours. The reaction mixture was cooled to room temperature. Cesiumcarbonate (0.162 g, 0.496 mmol) was added, and the reaction mixture wasstirred at room temperature for 45 minutes. The reaction mixture wasfiltered through Celite®, washed with acetone, and concentrated.Purification by flash column chromatography using 0-60% ethylacetate/hexanes as eluent provided the title compound as a pale orangesolid (1.790 g, 80%): mp 120-122° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.89 (s,1H), 7.24 (s, 1H), 7.20-7.01 (m, 2H), 4.20-3.99 (m, 2H), 2.36 (s, 3H);¹⁹F NMR (376 MHz, CDCl₃) δ −125.16; ESIMS m/z 225 ([M+H]⁺).

The following compounds were prepared in like manner to the procedureoutlined in Example 14:

2-Imino-3-(2-(1-methoxyethyl)-5-methylphenyl)thiazolidin-4-one (C51)

Prepared from 2-chloro-N-(2-(1-methoxyethyl)-5-methylphenyl)acetamide(C46) and isolated as an orange solid (1.80 g, 71%): mp 94-108° C.; ¹HNMR (300 MHz, CDCl₃) δ 7.51 (d, J=7.9 Hz, 1H), 7.34 (dd, J=8.0, 1.9 Hz,1H), 7.00-6.86 (m, 1H), 4.21-4.05 (m, 2H), 3.12 (d, J=1.1 Hz, 2H), 2.38(s, 3H), 1.42-1.31 (m, 3H); ¹³C NMR (75 MHz, CDCl₃) δ 210.86, 170.85,139.07, 131.65, 129.19, 129.06, 127.13, 77.52, 77.09, 76.67, 74.46,74.15, 69.51, 56.72, 56.54, 53.81, 31.76, 29.28, 23.35, 20.98.

2-Imino-3-(2-(methoxymethyl)-5-methylphenyl)thiazolidin-4-one (C52)

Prepared from 2-chloro-N-(2-(methoxymethyl)-5-methylphenyl)acetamide(C47) and isolated as an orange solid (0.550 g, 25%): mp 66-71° C.; ¹HNMR (400 MHz, CDCl₃) δ 9.37 (s, 1H), 8.00 (s, 1H), 7.07 (d, J=7.6 Hz,1H), 6.97-6.89 (m, 1H), 4.56 (s, 2H), 3.86 (s, 2H), 3.42 (s, 3H), 2.37(s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ 162.54, 139.50, 136.62, 129.24,125.51, 123.55, 122.35, 73.76, 57.85, 37.87, 21.45; EIMS m/z 250 ([M]⁺).

2-Imino-3-(5-methyl-2-propylphenyl)thiazolidin-4-one (C53)

Prepared from 2-chloro-N-(5-methyl-2-propylphenyl)acetamide (C48) andisolated as a white solid (1.76 g, 84%): mp 120-123° C.; ¹H NMR (400MHz, DMSO-d₆) δ 9.67 (s, 1H), 7.17 (d, J=1.7 Hz, 1H), 7.11 (d, J=7.7 Hz,1H), 7.00-6.93 (m, 1H), 4.11 (s, 2H), 2.52-2.48 (m, 2H), 2.25 (s, 3H),1.50 (h, J=7.4 Hz, 2H), 0.88 (t, J=7.3 Hz, 3H); ¹³C NMR (126 MHz,DMSO-d₆) δ 164.20, 134.56, 134.13, 132.75, 128.76, 126.11, 125.70,112.19, 36.01, 31.68, 22.32, 19.91, 13.23; EIMS m/z 248 ([M]⁺).

3-(4-Fluoro-2-isopropyl-5-methylphenyl)-2-iminothiazolidin-4-one (C54)

Prepared from 2-chloro-N-(4-fluoro-2-isopropyl-5-methylphenyl)acetamide(C49) and isolated as a brown oil (1.11 g, 80%): ¹H NMR (400 MHz, CDCl₃)δ 7.86 (s, 1H), 7.07 (d, J=10.7 Hz, 1H), 6.93 (d, J=7.3 Hz, 1H),4.12-4.00 (m, 2H), 2.72-2.59 (m, 1H), 2.25 (s, 3H), 1.17 (d, J=7.0 Hz,6H); ¹⁹F NMR (376 MHz, CDCl₃) 0-114.93; ESIMS m/z 267 ([M+H]⁺).

Example 15 Preparation of 1-(4-methyl-2-nitrophenyl)ethan-1-one (C55)

To a reaction flask were added4-methyl-2-nitro-1-(prop-1-en-2-yl)benzene (11.4 g, 64.3 mmol),dichloromethane (292 mL), and methanol (29.2 mL). The reaction mixturewas cooled to −78° C. Ozone was bubbled into the reaction mixture, andthe reaction mixture was stirred at −78° C. for 3 hours. The reactionmixture was flushed with nitrogen. Dimethylsulfide (14.0 mL, 189 mmol)was added, and the reaction mixture was allowed to stir and warm to roomtemperature overnight. The reaction was concentrated. Purification byflash column chromatography using ethyl acetate/hexanes as eluentprovided the title compound as an oil (8.90 g, 70%): ¹H NMR (300 MHz,CDCl₃) δ 7.85 (dt, J=2.0, 1.0 Hz, 1H), 7.50 (ddt, J=7.8, 1.7, 0.8 Hz,1H), 7.35 (dd, J=7.7, 0.9 Hz, 1H), 2.57-2.51 (m, 3H), 2.49 (q, J=0.9 Hz,3H).

Example 16 Preparation of 1-(4-methyl-2-nitrophenyl)ethan-1-ol (C56)

To a reaction flask under an atmosphere of nitrogen was added1-(4-methyl-2-nitrophenyl)ethan-1-one (C55) (8.91 g, 49.7 mmol) andmethanol (249 mL). The reaction mixture was cooled to 0° C. Sodiumborohydride (2.26 g, 59.7 mmol) was added, and the reaction mixture wasstirred at 0° C. for 1 hour. The reaction mixture was allowed to warm toroom temperature overnight. The reaction mixture was acidified withhydrochloric acid (2 N) and was diluted with dichloromethane. The layerswere separated, and the aqueous phase was extracted withdichloromethane. The combined organics were dried over sodium sulfate,filtered, and concentrated. Purification by flash column chromatographyusing ethyl acetate/hexanes as eluent provided the title compound as agreen oil (7.10 g, 75%): ¹H NMR (400 MHz, CDCl₃) δ 7.73-7.66 (m, 2H),7.45 (dd, J=8.0, 2.1 Hz, 1H), 5.45-5.26 (m, 1H), 2.42 (s, 3H), 1.54 (s,3H).

Example 17 Preparation of 1-(1-methoxyethyl)-4-methyl-2-nitrobenzene(C57)

To a dry round-bottomed flask were added1-(4-methyl-2-nitrophenyl)ethan-1-ol (C56) (6.14 g, 33.9 mmol) andtetrahydrofuran (169 mL). The reaction mixture was cooled to 0° C.Sodium hydride (60% oil immersion, 2.03 g, 50.8 mmol) was added under anatmosphere of nitrogen. The reaction mixture was stirred at 0° C. for 30minutes, then iodomethane (3.18 mL, 50.8 mmol) was added. The reactionmixture was allowed to warm to room temperature and stirred overnight.The reaction mixture was diluted with saturated aqueous ammoniumchloride, and water was added. The layers were separated, and theaqueous phase was extracted with dichloromethane (2×). The combinedorganic layers were dried over sodium sulfate, filtered, andconcentrated. Purification by flash column chromatography using ethylacetate/hexanes as eluent provided the title compound as a yellow oil(7.10 g, 98%): ¹H NMR (400 MHz, CHCl₃) δ 7.78-7.68 (m, 1H), 7.61 (d,J=8.0 Hz, 1H), 7.45 (ddd, J=8.1, 1.8, 0.9 Hz, 1H), 4.84 (q, J=6.3 Hz,1H), 3.19 (d, J=0.8 Hz, 3H), 2.43 (s, 3H), 1.50 (dd, J=6.3, 0.8 Hz, 3H);¹³C NMR (126 MHz, CDCl₃) δ 148.60, 138.44, 136.60, 134.47, 127.44,124.41, 77.49, 77.23, 76.98, 74.87, 56.82, 23.44, 20.75.

Example 18 Preparation of 2-(1-methoxyethyl)-5-methylaniline (C58)

To a reaction flask were added1-(1-methoxyethyl)-4-methyl-2-nitrobenzene (C57) (7.00 g, 35.9 mmol),nickel(II) chloride (4.65 g, 35.9 mmol), and methanol (179 mL). Sodiumborohydride (2.94 g, 78.0 mmol) was added to the reaction mixture in200-500 mg portions every 2-3 minutes under an atmosphere of nitrogen.The reaction mixture was quenched with acetone (6 mL) and wasconcentrated to approximately 80 mL. The crude mixture was diluted withdichloromethane and washed with water. The layers were separated, andthe organics were concentrated. Purification by flash columnchromatography using ethyl acetate/hexanes as eluent provided the titlecompound as an orange oil (2.99 g, 45%): ¹H NMR (300 MHz, CHCl₃) δ 6.87(d, J=7.6 Hz, 1H), 6.51 (ddd, J=7.5, 1.7, 0.8 Hz, 1H), 6.47 (d, J=1.6Hz, 1H), 4.36 (q, J=6.7 Hz, 1H), 4.22 (s, 2H), 3.26 (s, 3H), 2.24 (d,J=0.8 Hz, 3H), 1.56-1.46 (m, 3H); ¹³C NMR (126 MHz, CDCl₃) δ 144.87,128.61, 122.59, 118.56, 116.95, 80.41, 77.31, 77.06, 76.81, 55.93,21.09, 20.01.

Example 19 Preparation of 1-(methoxymethyl)-4-methyl-2-nitrobenzene(C59)

To (4-methyl-2-nitrophenyl)methanol (0.823 g, 4.92 mmol) intetrahydrofuran (20 mL) at 0° C. was added sodium hydride (60% oilimmersion, 0.217 g, 5.42 mmol) in small portions. Gas evolution wasimmediately observed. The reaction mixture was stirred for 30 minutes,and then iodomethane (0.460 mL, 7.39 mmol) was added. The reactionmixture was slowly warmed to room temperature overnight. The reactionmixture was quenched with methanol, and water and dichloromethane wereadded. The organic layer was filtered through a phase separator andconcentrated to provide the title compound as an orange wax (1.10 g,100%): ¹H NMR (400 MHz, CDCl₃) δ 7.88 (t, J=1.2 Hz, 1H), 7.63 (d, J=7.9Hz, 1H), 7.49-7.41 (m, 1H), 4.80 (s, 2H), 3.48 (s, 3H), 2.43 (s, 3H);¹³C NMR (126 MHz, CDCl₃) δ 156.37, 138.33, 134.42, 132.03, 128.47,124.97, 71.07, 58.87, 20.80; EIMS m/z 180 ([M]+).

It is recognized that some reagents and reaction conditions may not becompatible with certain functionalities that may be present in certainmolecules of Formula One or certain molecules used in the preparation ofcertain molecules of Formula One. In such cases, it may be necessary toemploy standard protection and deprotection protocols comprehensivelyreported in the literature and well known to a person skilled in theart. In addition, in some cases it may be necessary to perform furtherroutine synthetic steps not described herein to complete the synthesisof desired molecules. A person skilled in the art will also recognizethat it may be possible to achieve the synthesis of desired molecules byperforming some of the steps of the synthetic routes in a differentorder to that described. A person skilled in the art will also recognizethat it may be possible to perform standard functional groupinterconversions or substitution reactions on desired molecules tointroduce or modify substituents.

Biological Assays

The following bioassays against Beet Armyworm (Spodoptera exigua),Cabbage Looper (Trichoplusia ni), and Yellow Fever Mosquito (Aedesaegypti), are included herein due to the damage they inflict.Furthermore, the Beet Armyworm and Cabbage Looper are two good indicatorspecies for a broad range of chewing pests. Additionally, the GreenPeach Aphid is a good indicator species for a broad range of sap-feedingpests. The results with these four indicator species along with theYellow Fever Mosquito show the broad usefulness of the molecules ofFormula One in controlling pests in Phyla Arthropoda, Mollusca, andNematoda (Drewes et al.)

Example A Bioassays on Beet Armyworm (Spodoptera exigua, LAPHEG) (“BAW”)and Cabbage Looper (Trichoplusia ni, TRIPNI) (“CL”)

Beet armyworm is a serious pest of economic concern for alfalfa,asparagus, beets, citrus, corn, cotton, onions, peas, peppers, potatoes,soybeans, sugar beets, sunflowers, tobacco, and tomatoes, among othercrops. It is native to Southeast Asia but is now found in Africa,Australia, Japan, North America, and Southern Europe. The larvae mayfeed in large swarms causing devastating crop losses. It is known to beresistant to several pesticides.

Cabbage looper is a serious pest found throughout the world. It attacksalfalfa, beans, beets, broccoli, Brussel sprouts, cabbage, cantaloupe,cauliflower, celery, collards, cotton, cucumbers, eggplant, kale,lettuce, melons, mustard, parsley, peas, peppers, potatoes, soybeans,spinach, squash, tomatoes, turnips, and watermelons, among other crops.This species is very destructive to plants due to its voraciousappetite. The larvae consume three times their weight in food daily. Thefeeding sites are marked by large accumulations of sticky, wet, fecalmaterial, which may contribute to higher disease pressure therebycausing secondary problems on the plants in the site. It is known to beresistant to several pesticides.

Consequently, because of the above factors control of these pests isimportant. Furthermore, molecules that control these pests (BAW and CL),which are known as chewing pests, will be useful in controlling otherpests that chew on plants.

Certain molecules disclosed in this document were tested against BAW andCL using procedures described in the following examples. In thereporting of the results, the “BAW & CL Rating Table” was used (SeeTable Section).

Bioassays on BAW

Bioassays on BAW were conducted using a 128-well diet tray assay. One tofive second instar BAW larvae were placed in each well (3 mL) of thediet tray that had been previously filled with 1 mL of artificial dietto which 50 μg/cm² of the test molecule (dissolved in 50 μL of 90:10acetone-water mixture) had been applied (to each of eight wells) andthen allowed to dry. Trays were covered with a clear self-adhesivecover, vented to allow gas exchange, and held at 25° C., 14:10light-dark for five to seven days. Percent mortality was recorded forthe larvae in each well; activity in the eight wells was then averaged.The results are indicated in the table entitled “Table ABC: BiologicalResults” (See Table Section).

Bioassays on CL

Bioassays on CL were conducted using a 128-well diet tray assay. One tofive second instar CL larvae were placed in each well (3 mL) of the diettray that had been previously filled with 1 mL of artificial diet towhich 50 μg/cm² of the test molecule (dissolved in 50 μL of 90:10acetone-water mixture) had been applied (to each of eight wells) andthen allowed to dry. Trays were covered with a clear self-adhesivecover, vented to allow gas exchange, and held at 25° C., 14:10light-dark for five to seven days. Percent mortality was recorded forthe larvae in each well; activity in the eight wells was then averaged.The results are indicated in the table entitled “Table ABC: BiologicalResults” (See Table Section).

Example B Bioassays on Yellow Fever Mosquito (Aedes aegypti, AEDSAE)(“YFM”)

YFM prefers to feed on humans during the daytime and is most frequentlyfound in or near human habitations. YFM is a vector for transmittingseveral diseases. It is a mosquito that can spread the dengue fever andyellow fever viruses. Yellow fever is the second most dangerousmosquito-borne disease after malaria. Yellow fever is an acute viralhemorrhagic disease and up to 50% of severely affected persons withouttreatment will die from yellow fever. There are an estimated 200,000cases of yellow fever, causing 30,000 deaths worldwide each year. Denguefever is a nasty, viral disease; it is sometimes called “breakbonefever” or “break-heart fever” because of the intense pain it canproduce. Dengue fever kills about 20,000 people annually. Consequently,because of the above factors control of this pest is important.Furthermore, molecules that control this pest (YFM), which is known as asucking pest, are useful in controlling other pests that cause human andanimal suffering.

Certain molecules disclosed in this document were tested against YFMusing procedures described in the following paragraph. In the reportingof the results, the “YFM Rating Table” was used (See Table Section).

Master plates containing 400 μg of a molecule dissolved in 100 μL ofdimethyl sulfoxide (DMSO) (equivalent to a 4000 ppm solution) are used.A master plate of assembled molecules contains 15 μL per well. To thisplate, 135 μL of a 90:10 water/acetone mixture is added to each well. Arobot (Biomek® NXP Laboratory Automation Workstation) is programmed todispense 15 μL aspirations from the master plate into an empty 96-wellshallow plate (“daughter” plate). There are 6 reps (“daughter” plates)created per master. The created “daughter” plates are then immediatelyinfested with YFM larvae.

The day before plates are to be treated, mosquito eggs are placed inMillipore water containing liver powder to begin hatching (4 g into 400mL). After the “daughter” plates are created using the robot, they areinfested with 220 μL of the liver powder/larval mosquito mixture (about1 day-old larvae). After plates are infested with mosquito larvae, anon-evaporative lid is used to cover the plate to reduce drying. Platesare held at room temperature for 3 days prior to grading. After 3 days,each well is observed and scored based on mortality. The results areindicated in the table entitled “Table ABC: Biological Results” (SeeTable Section).

Agriculturally Acceptable Acid Addition Salts, Salt Derivatives,Solvates, Ester Derivatives, Polymorphs, Isotopes, and Radionuclides

Molecules of Formula One may be formulated into agriculturallyacceptable acid addition salts. By way of a non-limiting example, anamine function can form salts with hydrochloric, hydrobromic, sulfuric,phosphoric, acetic, benzoic, citric, malonic, salicylic, malic, fumaric,oxalic, succinic, tartaric, lactic, gluconic, ascorbic, maleic,aspartic, benzenesulfonic, methanesulfonic, ethanesulfonic,hydroxyl-methanesulfonic, and hydroxyethanesulfonic acids. Additionally,by way of a non-limiting example, an acid function can form saltsincluding those derived from alkali or alkaline earth metals and thosederived from ammonia and amines. Examples of preferred cations includesodium, potassium, and magnesium.

Molecules of Formula One may be formulated into salt derivatives. By wayof a non-limiting example, a salt derivative may be prepared bycontacting a free base with a sufficient amount of the desired acid toproduce a salt. A free base may be regenerated by treating the salt witha suitable dilute aqueous base solution such as dilute aqueous sodiumhydroxide, potassium carbonate, ammonia, and sodium bicarbonate. As anexample, in many cases, a pesticide, such as 2,4-D, is made morewater-soluble by converting it to its dimethylamine salt.

Molecules of Formula One may be formulated into stable complexes with asolvent, such that the complex remains intact after the non-complexedsolvent is removed. These complexes are often referred to as “solvates.”However, it is particularly desirable to form stable hydrates with wateras the solvent.

Molecules of Formula One containing an acid functionality may be madeinto ester derivatives. These ester derivatives can then be applied inthe same manner as the molecules disclosed in this document are applied.

Molecules of Formula One may be made as various crystal polymorphs.

Polymorphism is important in the development of agrochemicals sincedifferent crystal polymorphs or structures of the same molecule can havevastly different physical properties and biological performances.

Molecules of Formula One may be made with different isotopes. Ofparticular importance are molecules having ²H (also known as deuterium)or ³H (also known as tritium) in place of ¹H. Molecules of Formula Onemay be made with different radionuclides. Of particular importance aremolecules having ¹⁴C (also known as radiocarbon). Molecules of FormulaOne having deuterium, tritium, or ¹⁴C may be used in biological studiesallowing tracing in chemical and physiological processes and half-lifestudies, as well as, MoA studies.

Combinations

In another embodiment of this invention, molecules of Formula One may beused in combination (such as, in a compositional mixture, or asimultaneous or sequential application) with one or more activeingredients.

In another embodiment of this invention, molecules of Formula One may beused in combination (such as, in a compositional mixture, or asimultaneous or sequential application) with one or more activeingredients each having a MoA that is the same as, similar to, but morelikely—different from, the MoA of the molecules of Formula One.

In another embodiment, molecules of Formula One may be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more molecules having acaricidal,algicidal, avicidal, bactericidal, fungicidal, herbicidal, insecticidal,molluscicidal, nematicidal, rodenticidal, and/or virucidal properties.

In another embodiment, the molecules of Formula One may be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more molecules that areantifeedants, bird repellents, chemosterilants, herbicide safeners,insect attractants, insect repellents, mammal repellents, matingdisrupters, plant activators, plant growth regulators, and/orsynergists.

In another embodiment, molecules of Formula One may also be used incombination (such as in a compositional mixture, or a simultaneous orsequential application) with one or more biopesticides.

In another embodiment, in a pesticidal composition combinations of amolecule of Formula One and an active ingredient may be used in a widevariety of weight ratios. For example, in a two-component mixture, theweight ratio of a molecule of Formula One to an active ingredient, theweight ratios in Table B may be used. However, in general, weight ratiosless than about 10:1 to about 1:10 are preferred. It is also preferredsometimes to use a three, four, five, six, seven, or more, componentmixture comprising a molecule of Formula One and an additional two ormore active ingredients.

Weight ratios of a molecule of Formula One to an active ingredient mayalso be depicted as X:Y; wherein X is the parts by weight of a moleculeof Formula One and Y is the parts by weight of active ingredient. Thenumerical range of the parts by weight for X is 0<X≦100 and the parts byweight for Y is 0<Y≦100 and is shown graphically in TABLE C. By way ofnon-limiting example, the weight ratio of a molecule of Formula One toan active ingredient may be 20:1.

Ranges of weight ratios of a molecule of Formula One to an activeingredient may be depicted as X₁:Y₁ to X₂:Y₂, wherein X and Y aredefined as above.

In one embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁>Y₁ and X₂<Y₂. By way of non-limiting example, the range of aweight ratio of a molecule of Formula One to an active ingredient may bebetween 3:1 and 1:3, inclusive of the endpoints.

In another embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁>Y₁ and X₂>Y₂. By way of non-limiting example, the range ofweight ratio of a molecule of Formula One to an active ingredient may bebetween 15:1 and 3:1, inclusive of the endpoints.

In another embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁<Y₁ and X₂<Y₂. By way of non-limiting example, the range ofweight ratios of a molecule of Formula One to an active ingredient maybe between about 1:3 and about 1:20, inclusive of the endpoints.

It is envisioned that certain weight ratios of a molecule of Formula Oneto an active ingredient, as presented in Table B and C, may besynergistic.

Formulations

A pesticide is many times not suitable for application in its pure form.It is usually necessary to add other substances so that the pesticidemay be used at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticide activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra-low volume solutions.

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations areeither solids, usually known as wettable powders, water dispersiblegranules, liquids usually known as emulsifiable concentrates, or aqueoussuspensions. Wettable powders, which may be compacted to form waterdispersible granules, comprise an intimate mixture of the pesticide, acarrier, and surfactants. The concentration of the pesticide is usuallyfrom about 10% to about 90% by weight. The carrier is usually selectedfrom among the attapulgite clays, the montmorillonite clays, thediatomaceous earths, or the purified silicates. Effective surfactants,comprising from about 0.5% to about 10% of the wettable powder, arefound among sulfonated lignins, condensed naphthalenesulfonates,naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, andnon-ionic surfactants such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are selected from conventionalanionic and non-ionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums may, also be added to increase the density andviscosity of the aqueous carrier. It is often most effective to grindand mix the pesticide at the same time by preparing the aqueous mixtureand homogenizing it in an implement such as a sand mill, ball mill, orpiston-type homogenizer. The pesticide in suspension might bemicroencapsulated in plastic polymer.

Oil dispersions (OD) comprise suspensions of organic solvent-insolublepesticides finely dispersed in a mixture of organic solvent andemulsifiers at a concentration in the range from about 2% to about 50%by weight. One or more pesticide might be dissolved in the organicsolvent. Useful organic solvents include aromatics, especially xylenesand petroleum fractions, especially the high-boiling naphthalenic andolefinic portions of petroleum such as heavy aromatic naphtha. Othersolvents may include vegetable oils, seed oils, and esters of vegetableand seed oils. Suitable emulsifiers for oil dispersions are selectedfrom conventional anionic and non-ionic surfactants. Thickeners orgelling agents are added in the formulation of oil dispersions to modifythe rheology or flow properties of the liquid and to prevent separationand settling of the dispersed particles or droplets.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier, which has beenpre-formed to the appropriate particle size, in the range of from about0.5 mm to about 3 mm. Such compositions may also be formulated by makinga dough or paste of the carrier and molecule, and then crushing anddrying to obtain the desired granular particle size. Another form ofgranules is a water emulsifiable granule (EG). It is a formulationconsisting of granules to be applied as a conventional oil-in-wateremulsion of the active ingredient(s), either solubilized or diluted inan organic solvent, after disintegration and dissolution in water. Wateremulsifiable granules comprise one or several active ingredient(s),either solubilized or diluted in a suitable organic solvent that is(are) absorbed in a water soluble polymeric shell or some other type ofsoluble or insoluble matrix.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. Dusts maybe applied as a seed dressing or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions, the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait, they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. Baits may be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings, or in special chambers.

Pesticides may be microencapsulated by suspending the pesticideparticles or droplets in plastic polymers of various types. By altering,the chemistry of the polymer or by changing factors in the processing,microcapsules may be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which inturn, affects the residual performance, speed of action, and odor of theproduct. The microcapsules might be formulated as suspensionconcentrates or water dispersible granules.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one molecule which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent, and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers.

Other Formulation Components

Generally, when the molecules disclosed in Formula One are used in aformulation, such formulation can also contain other components. Thesecomponents include, but are not limited to, (this is a non-exhaustiveand non-mutually exclusive list) wetters, spreaders, stickers,penetrants, buffers, sequestering agents, drift reduction agents,compatibility agents, anti-foam agents, cleaning agents, andemulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulfate,sodium dioctyl sulfosuccinate, alkyl phenol ethoxylates, and aliphaticalcohol ethoxylates.

A dispersing agent is a substance that adsorbs onto the surface ofparticles, helps to preserve the state of dispersion of the particles,and prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates, and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulfonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such assodium-naphthalene-sulfonate-formaldehyde-condensates. Tristyrylphenolethoxylate phosphate esters are also used. Non-ionics such asalkylarylethylene oxide condensates and EO-PO block copolymers aresometimes combined with anionics as dispersing agents for suspensionconcentrates. In recent years, new types of very high molecular weightpolymeric surfactants have been developed as dispersing agents. Thesehave very long hydrophobic ‘backbones’ and a large number of ethyleneoxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These highmolecular weight polymers can give very good long-term stability tosuspension concentrates because the hydrophobic backbones have manyanchoring points onto the particle surfaces. Examples of dispersingagents used in agrochemical formulations are: sodium lignosulfonates,sodium naphthalene sulfonate formaldehyde condensates,tristyrylphenol-ethoxylate-phosphate-esters, aliphatic alcoholethoxylates, alkyl ethoxylates, EO-PO block copolymers, and graftcopolymers.

An emulsifying agent is a substance that stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent, the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends contain analkylphenol or an aliphatic alcohol with twelve or more ethylene oxideunits and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from about 8 toabout 18 will normally provide good stable emulsions. Emulsion stabilitycan sometimes be improved by the addition of a small amount of an EO-POblock copolymer surfactant.

A solubilizing agent is a surfactant that will form micelles in water atconcentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics, sorbitan monooleates, sorbitanmonooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alkyl ethoxylates, linear aliphatic alcoholethoxylates, and aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules, and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, oil-in-water emulsions, suspoemulsions, oil dispersions,and ultra-low volume formulations, and to a lesser extent, granularformulations. Sometimes mixtures of solvents are used. The first maingroups of solvents are aliphatic paraffinic oils such as kerosene orrefined paraffins. The second main group (and the most common) comprisesthe aromatic solvents such as xylene and higher molecular weightfractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons areuseful as cosolvents to prevent crystallization of pesticides when theformulation is emulsified into water. Alcohols are sometimes used ascosolvents to increase solvent power. Other solvents may includevegetable oils, seed oils, and esters of vegetable and seed oils.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, oil dispersions, emulsions and suspoemulsionsto modify the rheology or flow properties of the liquid and to preventseparation and settling of the dispersed particles or droplets.Thickening, gelling, and anti-settling agents generally fall into twocategories, namely water-insoluble particulates and water-solublepolymers. It is possible to produce suspension concentrate and oildispersion formulations using clays and silicas. Examples of these typesof materials, include, but are not limited to, montmorillonite,bentonite, magnesium aluminum silicate, and attapulgite. Water-solublepolysaccharides in water based suspension concentrates have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum, carrageenam,alginates, methyl cellulose, sodium carboxymethyl cellulose (SCMC), andhydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol, andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Therefore,preservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt, sorbic acid and its sodium or potassium salts,benzoic acid and its sodium salt, p-hydroxybenzoic acid sodium salt,methyl p-hydroxybenzoate, and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations tofoam during mixing operations in production and in application through aspray tank. In order to reduce the tendency to foam, anti-foam agentsare often added either during the production stage or before fillinginto bottles. Generally, there are two types of anti-foam agents, namelysilicones and non-silicones. Silicones are usually aqueous emulsions ofdimethyl polysiloxane, while the non-silicone anti-foam agents arewater-insoluble oils, such as octanol and nonanol, or silica. In bothcases, the function of the anti-foam agent is to displace the surfactantfrom the air-water interface.

“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce theoverall environmental footprint of crop protection formulations. Greenagents are biodegradable and generally derived from natural and/orsustainable sources, e.g. plant and animal sources. Specific examplesare: vegetable oils, seed oils, and esters thereof, also alkoxylatedalkyl polyglucosides.

Applications

Molecules of Formula One may be applied to any locus. Particular loci toapply such molecules include loci where alfalfa, almonds, apples,barley, beans, canola, corn, cotton, crucifers, flowers, fodder species(Rye Grass, Sudan Grass, Tall Fescue, Kentucky Blue Grass, and Clover),fruits, lettuce, oats, oil seed crops, oranges, peanuts, pears, peppers,potatoes, rice, sorghum, soybeans, strawberries, sugarcane, sugarbeets,sunflowers, tobacco, tomatoes, wheat (for example, Hard Red WinterWheat, Soft Red Winter Wheat, White Winter Wheat, Hard Red Spring Wheat,and Durum Spring Wheat), and other valuable crops are growing or theseeds thereof are going to be planted.

Molecules of Formula One may also be applied where plants, such ascrops, are growing and where there are low levels (even no actualpresence) of pests that can commercially damage such plants. Applyingsuch molecules in such locus is to benefit the plants being grown insuch locus. Such benefits, may include, but are not limited to: helpingthe plant grow a better root system; helping the plant better withstandstressful growing conditions; improving the health of a plant; improvingthe yield of a plant (e.g. increased biomass and/or increased content ofvaluable ingredients); improving the vigor of a plant (e.g. improvedplant growth and/or greener leaves); improving the quality of a plant(e.g. improved content or composition of certain ingredients); andimproving the tolerance to abiotic and/or biotic stress of the plant.

Molecules of Formula One may be applied with ammonium sulfate whengrowing various plants as this may provide additional benefits.

Molecules of Formula One may be applied on, in, or around plantsgenetically modified to express specialized traits, such as Bacillusthuringiensis (for example, Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab,Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1/Cry35Ab1), other insecticidaltoxins, or those expressing herbicide tolerance, or those with “stacked”foreign genes expressing insecticidal toxins, herbicide tolerance,nutrition-enhancement, or any other beneficial traits.

Molecules of Formula One may be applied to the foliar and/or fruitingportions of plants to control pests. Either such molecules will come indirect contact with the pest, or the pest will consume such moleculeswhen eating the plant or while extracting sap or other nutrients fromthe plant.

Molecules of Formula One may also be applied to the soil, and whenapplied in this manner, root and stem feeding pests may be controlled.The roots may absorb such molecules thereby taking it up into the foliarportions of the plant to control above ground chewing and sap feedingpests.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying (for example by spraying alocus) a molecule of Formula One to a different portion of the plant.For example, control of foliar-feeding insects may be achieved by dripirrigation or furrow application, by treating the soil with for examplepre- or post-planting soil drench, or by treating the seeds of a plantbefore planting.

Molecules of Formula One may be used with baits. Generally, with baits,the baits are placed in the ground where, for example, termites can comeinto contact with, and/or be attracted to, the bait. Baits can also beapplied to a surface of a building, (horizontal, vertical, or slantsurface) where, for example, ants, termites, cockroaches, and flies, cancome into contact with, and/or be attracted to, the bait.

Molecules of Formula One may be encapsulated inside, or placed on thesurface of a capsule. The size of the capsules can range from nanometersize (about 100-900 nanometers in diameter) to micrometer size (about10-900 microns in diameter).

Molecules of Formula One may be applied to eggs of pests. Because of theunique ability of the eggs of some pests to resist certain pesticides,repeated applications of such molecules may be desirable to controlnewly emerged larvae.

Molecules of Formula One may be applied as seed treatments. Seedtreatments may be applied to all types of seeds, including those fromwhich plants genetically modified to express specialized traits willgerminate. Representative examples include those expressing proteinstoxic to invertebrate pests, such as Bacillus thuringiensis or otherinsecticidal toxins, those expressing herbicide tolerance, such as“Roundup Ready” seed, or those with “stacked” foreign genes expressinginsecticidal toxins, herbicide tolerance, nutrition-enhancement, droughttolerance, or any other beneficial traits. Furthermore, such seedtreatments with molecules of Formula One may further enhance the abilityof a plant to withstand stressful growing conditions better. Thisresults in a healthier, more vigorous plant, which can lead to higheryields at harvest time. Generally, about 1 gram of such molecules toabout 500 grams per 100,000 seeds is expected to provide good benefits,amounts from about 10 grams to about 100 grams per 100,000 seeds isexpected to provide better benefits, and amounts from about 25 grams toabout 75 grams per 100,000 seeds is expected to provide even betterbenefits. Molecules of Formula One may be applied with one or moreactive ingredients in a soil amendment.

Molecules of Formula One may be used for controlling endoparasites andectoparasites in the veterinary medicine sector or in the field ofnon-human-animal keeping. Such molecules may be applied by oraladministration in the form of, for example, tablets, capsules, drinks,granules, by dermal application in the form of, for example, dipping,spraying, pouring on, spotting on, and dusting, and by parenteraladministration in the form of, for example, an injection.

Molecules of Formula One may also be employed advantageously inlivestock keeping, for example, cattle, chickens, geese, goats, pigs,sheep, and turkeys. They may also be employed advantageously in petssuch as, horses, dogs, and cats. Particular pests to control would beflies, fleas, and ticks that are bothersome to such animals. Suitableformulations are administered orally to the animals with the drinkingwater or feed. The dosages and formulations that are suitable depend onthe species.

Molecules of Formula One may also be used for controlling parasiticworms, especially of the intestine, in the animals listed above.

Molecules of Formula One may also be employed in therapeutic methods forhuman health care. Such methods include, but are limited to, oraladministration in the form of, for example, tablets, capsules, drinks,granules, and by dermal application.

Molecules of Formula One may also be applied to invasive pests. Pestsaround the world have been migrating to new environments (for such pest)and thereafter becoming a new invasive species in such new environment.Such molecules may also be used on such new invasive species to controlthem in such new environments.

Before a pesticide may be used or sold commercially, such pesticideundergoes lengthy evaluation processes by various governmentalauthorities (local, regional, state, national, and international).Voluminous data requirements are specified by regulatory authorities andmust be addressed through data generation and submission by the productregistrant or by a third party on the product registrant's behalf, oftenusing a computer with a connection to the World Wide Web. Thesegovernmental authorities then review such data and if a determination ofsafety is concluded, provide the potential user or seller with productregistration approval. Thereafter, in that locality where the productregistration is granted and supported, such user or seller may use orsell such pesticide.

Molecules according to Formula One may be tested to determine itsefficacy against pests. Additionally, a molecule of Formula One may bemixed with another active ingredient to form a pesticidal composition,and then that composition is tested to determine if it is synergisticusing conventional testing procedures. Furthermore, mode of actionstudies may be conducted to determine if said molecule has a differentmode of action than other pesticides. Thereafter, such acquired data maybe disseminated, such as by the internet, to third parties.

The headings in this document are for convenience only and must not beused to interpret any portion hereof.

Tables

TABLE B Weight Ratios Molecule of the Formula One:active Ingredient100:1 to 1:100 50:1 to 1:50 20:1 to 1:20 10:1 to 1:10 5:1 to 1:5 3:1 to1:3 2:1 to 1:2 1:1

TABLE C active ingredient 100 X, Y X, Y X, Y (Y) Parts by weight 50 X, YX, Y X, Y X, Y X, Y 20 X, Y X, Y X, Y X, Y X, Y 15 X, Y X, Y X, Y X, YX, Y 10 X, Y X, Y 5 X, Y X, Y X, Y X, Y 3 X, Y X, Y X, Y X, Y X, Y X, YX, Y 2 X, Y X, Y X, Y X, Y X, Y 1 X, Y X, Y X, Y X, Y X, Y X, Y X, Y X,Y X, Y 1 2 3 5 10 15 20 50 100 molecule of Formula One (X) Parts byweight

TABLE 2 Structure and preparation method for F Series molecules No.Structure Prep.* F1

5, 6 F2

6 F3

6 F4

6 F5

6 F6

6 F7

6 F8

6 F9

6 F10

6 F11

6 F12

5 F13

6 F14

6 F15

5 F16

6 F17

6 F18

6 F19

6 F20

5 F21

5 F22

6 F23

6 F24

6 F25

6 F26

6 F27

6 F28

6 F29

6 F30

6 F31

6 F32

6 F33

6 F34

6 F35

6 F36

6 F37

6 F38

6 F39

6 F40

6 F41

6 F42

6 F43

6 F44

6 F45

6 F46

6 *prepared according to example number

TABLE 3 Structure and preparation method for C series molecules No.Structure Prep* C1

1 C2

2 C3

2 C4

2 C5

2 C6

2 C7

3 C8

3 C9

3 C10

3 C11

3 C12

3 C13

3 C14

3 C15

3 C16

3 C17

3 C18

3 C19

3 C20

3 C21

3 C22

3 C23

4 C24

4 C25

4 C26

4 C27

4 C28

7 C29

8 C30

9 C31

10 C32

10 C33

10 C34

10 C35

10 C36

10 C37

10 C38

10 C39

10 C40

10 C41

10 C42

11 C43

12 C44

12 C45

13 C46

13 C47

13 C48

13 C49

13 C50

14 C51

14 C52

14 C53

14 C54

14 C55

15 C56

16 C57

17 C58

18 C59

19 *prepared according to example number

TABLE 4 Analytical data for molecules in Table 2 Mp ¹³CNMR; No. (° C.)Mass (m/z) ¹H NMR ¹⁹F NMR F1 215-225 ESIMS 625 (400 MHz, CDCl₃) δ ¹³CNMR (126 MHz, CDCl₃) ([M + H]⁺) 8.22 (s, 1H), δ 172.50, 170.20, 169.03,7.67-7.62 (m, 2H), 159.49, 147.99, 143.27, 7.54-7.47 (m, 2H), 7.43 (d, J= 8.7 Hz, 139.97, 137.98, 136.92, 2H), 135.49, 132.48, 131.45, 7.40-7.27(m, 5H), 131.23, 129.10, 128.58, 6.96-6.86 (m, 1H), 5.34 (s, 126.74,122.35, 121.40, 2H), 3.96 (d, J = 2.8 Hz, 120.41, 119.35, 118.71, 2H),2.65 (h, J = 7.0 Hz, 71.19, 33.00, 28.38, 23.81, 1H), 2.38 (s, 23.78,20.83; 3H), 1.18 (dd, J = 6.9, ¹⁹F NMR (471 MHz, CDCl₃) 3.6 Hz, 6H) δ−58.06 F2 201-203 ESIMS 643 (300 MHz, CDCl₃) δ ¹⁹F NMR (282 MHz, CDCl₃)([M + H]⁺) 8.37-8.31 (m, 1H), δ −58.06 8.24 (s, 1H), 7.64 (d, J = 9.3Hz, 2H), 7.35-7.26 (m, 5H), 7.26 (d, J = 5.1 Hz, 2H), 6.81 (s, 1H), 5.33(s, 2H), 3.97 (s, 2H), 2.69-2.60 (m, 1H), 2.38 (s, 3H), 1.29-1.16 (m,6H) F3 221-223 ESIMS 643 (300 MHz, CDCl₃) δ ¹⁹F NMR (282 MHz, CDCl₃)([M + H]⁺) 8.23 (s, 1H), 7.66 (d, J = 8.7 Hz, δ −58.06 2H), 7.57-7.52(m, 1H), 7.48-7.43 (m, 1H), 7.35-7.26 (m, 5H), 7.80 (d, J = 9.0 Hz, 1H),6.90 (s, 1H), 5.40 (s, 2H), 3.97 (d, J = 1.5 Hz, 2H), 2.68-2.63 (m, 1H),2.38 (s, 3H), 1.18 (d, J = 3.0 Hz, 6H) F4 171-173 ESIMS 653 (300 MHz,CDCl₃) δ ¹⁹F NMR (282 MHz, CDCl₃) ([M + H]⁺) 8.23 (s, 1H), 7.67 (d, J =9.0 Hz, δ −58.07 2H), 7.41-7.26 (m, 7H), 6.91 (s, 1H), 6.84 (dd, J =1.5, 6.0 Hz, 1H), 5.38 (s, 2H), 3.96 (s, 2H), 3.87 (s, 3H), 2.69-2.66(m, 1H), 2.38 (s, 3H), 1.25-1.16 (m, 6H) F5 209-211 ESIMS 625 (300 MHz,CDCl₃) δ ([M + H]⁺) 8.23 (s, 1H), 7.65 (d, J = 9.2 Hz, 2H), 7.50 (d, J =8.7 Hz, 2H), 7.42 (d, J = 8.7 Hz, 2H), 7.35-7.31 (m, 2H), 7.28-7.26 (m,3H), 6.93 (br s, 1H), 5.34 (s, 2H), 3.95 (d, J = 1.5 Hz, 2H), 2.38 (s,5H), 1.59-1.57 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H) F6 180-182 ESIMS 643(300 MHz, CDCl₃) δ ¹⁹F NMR (282 MHz, CDCl₃) δ ([M + H]⁺) 8.36-8.32 (m,1H), δ −58.07 8.23 (s, 1H), 7.65 (d, J = 9.2 Hz, 2H), 7.41 (s, 1H), 7.33(d, J = 6.6 Hz, 2H), 7.32-7.22 (m, 4H), 6.91 (s, 1H), 5.33 (s, 2H), 3.96(d, J = 1.8 Hz, 2H), 2.38-2.34 (m, 5H), 1.60-1.54 (m, 2H), 0.89 (t, J =9.3 Hz, 3H) F7 202-204 ESIMS 643 (300 MHz, CDCl₃) δ ([M + H]⁺) 8.25 (s,1H), 7.66 (d, J = 9.17 Hz, 2H), 7.62-7.40 (m, 2H), 7.36-7.26 (m, 5H),7.10-7.03 (m, 1H), 6.93-6.90 (m, 1H), 5.40 (s, 2H), 3.97 (d, J = 1.47Hz, 2H), 2.40-2.38 (m, 5H), 1.56-1.51 (m, 2H), 0.91 (t, J = 7.34 Hz, 3H)F8 212-214 ESIMS 627 (300 MHz, CDCl₃) δ ([M + H]⁺) 8.23 (s, 1H),7.67-7.63 (m, 2H), 7.52-7.48 (m, 2H), 7.45-7.40 (m, 3H), 7.35-7.28 (m,4H), 7.00 (br s, 1H), 5.33 (s, 2H), 4.39-4.25 (m, 2H), 3.93 (d, J = 2.1Hz, 2H), 3.28 (s, 3H), 2.42 (s, 3H) F9 212-214 ESIMS 645 (300 MHz,CDCl₃) δ ([M + H]⁺) 8.24 (s, 1H), 7.69-7.63 (m, 2H), 7.57-7.51 (m, 1H),7.47-7.39 (m, 2H), 7.36-7.26 (m, 4H), 7.08-7.06 (m, 1H), 7.00 (br s,1H), 5.40 (s, 2H), 4.40-4.23 (m, 2H), 3.94 (d, J = 2.2 Hz, 2H), 3.27 (s,3H), 2.42 (s, 3H) F10 155-157 ESIMS 655 (300 MHz, CDCl₃) δ ([M + H]⁺)8.26 (s, 1H), 7.67-7.62 (m, 3H), 7.38-7.26 (m, 6H), 6.93 (br s, 1H),6.76-6.73 (m, 1H), 4.97 (s, 2H), 3.97 (d, J = 1.4 Hz, 2H), 3.93 (s, 3H),2.41-2.32 (m, 5H), 1.62-1.58 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H) F11161-163 ESIMS 657 (400 MHz, CDCl₃) δ ([M + H]⁺) 8.29 (s, 1H), 7.67-7.65(m, 2H), 7.61 (d, J = 2.0 Hz, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.35-7.29(m, 5H), 7.00 (br s, 1H), 6.73-6.71 (m, 1H), 4.96 (s, 2H), 4.36 (d, J =12.4 Hz, 1H), 4.27 (d, J = 12.8 Hz, 1H), 3.96-3.89 (m, 5H), 3.27 (s,3H), 2.42 (s, 3H) F12 ESIMS 661 (400 MHz, CDCl₃) δ ¹⁹F NMR (376 MHz,CDCl₃) ([M + H]⁺) 8.33 (t, J = 8.4 Hz, 1H), δ −58.07, −114.44, −131.028.24 (s, 1H), 7.69-7.61 (m, 2H), 7.42 (s, 1H), 7.38-7.30 (m, 2H), 7.23(d, J = 7.5 Hz, 1H), 7.10 (d, J = 10.7 Hz, 1H), 6.91 (d, J = 7.1 Hz,1H), 5.33 (s, 2H), 3.97 (d, J = 2.3 Hz, 2H), 2.61 (p, J = 6.9, 6.5 Hz,1H), 2.35-2.22 (m, 3H), 1.26 (d, J = 1.9 Hz, 1H), 1.17 (dd, J = 6.9, 3.9Hz, 6H) F13 214-216 ESIMS 626 (300 MHz, CDCl₃) δ ¹⁹F NMR (282 MHz,CDCl₃) ([M + H]⁺) 9.99 (s, 1H), 9.08 (s, δ −58.07 1H), 8.38 (s, 1H),7.92 (d, J = 8.7 Hz, 4H), 7.57 (d, J = 9.0 Hz, 2H), 7.29-7.20 (m, 2H),7.06 (s, 1H), 5.31 (s, 2H), 4.28-4.06 (m, 2H), 2.36-2.31 (m, 5H),1.52-1.44 (m, 2H), 0.83 (t, J = 7.2 Hz, 3H) F14 231-233 ESIMS 626 (300MHz, CDCl₃) δ ¹⁹F NMR (282 MHz, CDCl₃) ([M + H]⁺) 8.36 (s, 1H), 8.23 (s,δ −58.06 1H), 8.18 (d, J = 7.0 Hz, 1H), 7.87-7.84 (m, 2H), 7.64 (d, J =7.6 Hz, 2H), 7.36-7.30 (m, 4H), 6.86 (s, 1H), 5.34 (s, 2H), 4.03-3.93(m, 2H), 2.66-2.59 (m, 1H), 2.36 (s, 3H), 1.16 (d, J = 5.6 Hz, 6H) F15210-220 ESIMS 625 (400 MHz, CDCl₃) δ ¹³C NMR (126 MHz, CDCl₃) ([M + H]⁺)8.52 (s, 1H), δ 172.55, 169.62, 161.56, 7.78-7.64 (m, 2H), 159.45,154.87, 148.62, 7.44-7.29 (m, 6H), 7.16 (s, 143.29, 141.69, 136.89, 1H),7.04-6.95 (m, 135.26, 132.53, 131.68, 2H), 6.90 (dd, J = 1.8, 131.20,128.60, 126.72, 1.1 Hz, 1H), 5.20 (s, 122.37, 121.47, 120.44, 2H), 3.95(d, J = 2.7 Hz, 119.33, 115.38, 63.56, 2H), 2.67 (p, J = 6.8 Hz, 33.01,28.37, 23.82, 1H), 2.38 (s, 20.83; 3H), 1.18 (dd, J = 6.8, ¹⁹F NMR (376MHz, CDCl₃) 4.0 Hz, 6H) δ −58.03 F16 169-171 ESIMS 643 (400 MHz, CDCl₃)δ ¹⁹F NMR (376 MHz, CDCl₃) ([M + H]⁺) 8.52 (s, 1H), δ −58.07, −127.768.25-8.05 (m, 1H), 7.78-7.65 (m, 2H), 7.36 (d, J = 7.6 Hz, 3H), 7.30 (d,J = 7.6 Hz, 1H), 7.23 (s, 1H), 6.88 (s, 1H), 6.85-6.79 (m, 2H), 5.19 (s,2H), 3.95 (d, J = 2.0 Hz, 2H), 2.68-2.61 (m, 1H), 2.38 (s, 3H), 1.18 (t,J = 6.6 Hz, 6H) F17 159-161 ESIMS 625 (400 MHz, CDCl₃) δ ¹⁹F NMR (376MHz, CDCl₃) ([M + H]⁺) 8.52 (s, 1H), 7.71 (dd, J = 2.0, δ −58.07 6.8 Hz,2H), 7.42-7.28 (m, 4H), 7.30-7.24 (m, 2H), 7.15 (s, 1H), 7.00 (d, J =9.3 Hz, 2H), 6.92 (s, 1H), 5.20 (s, 2H), 3.94 (d, J = 2.9 Hz, 2H), 2.38(s, 5H), 1.55 (m, 2H), 0.91 (t, J = 4.5 Hz, 3H) F18 188-191 ESIMS 662(300 MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.34 (s, 1H),9.10 (s, d₆) δ −56.95, −117.16 1H), 7.99 (d, J = 9.2 Hz, 2H), 7.60 (d, J= 8.4 Hz, 2H), 7.38 (d, J = 8.1 Hz, 1H), 7.25 (d, J = 8.1 Hz, 1H), 7.06(s, 1H), 6.91 (d, J = 10.6 Hz, 2H), 5.25 (s, 2H), 4.21-4.01 (m, 2H),2.67 (td, J = 6.7, 13.8 Hz, 1H), 2.30 (s, 3H), 1.17-1.08 (m, 6H) F19182-185 ESIMS 664 (300 MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M +H]⁺) 9.34 (s, 1H), 9.10 (s, d₆) δ −56.957, −117.12 1H), 7.60 (d, J = 8.4Hz, 3H), 7.41 (d, J = 7.7 Hz, 1H), 7.29 (d, J = 7.3 Hz, 1H), 7.16 (s,1H), 6.92 (d, J = 9.5 Hz, 2H), 5.25 (s, 2H), 4.27 (s, 2H), 4.14-3.99 (m,3H), 3.21 (s, 3H), 2.35 (s, 3H) F20 ESIMS 659 (400 MHz, CDCl₃) δ ¹⁹F NMR(376 MHz, CDCl₃) ([M + H]⁺) 8.51 (s, 1H), δ −58.05, −127.86, −128.238.20-8.06 (m, 1H), 7.71 (d, J = 8.8 Hz, 2H), 7.51 (dd, J = 8.0, 3.2 Hz,1H), 7.36 (d, J = 8.5 Hz, 3H), 6.91 (s, 1H), 6.83 (t, J = 11.0 Hz, 2H),5.19 (s, 2H), 4.19-4.07 (m, 2H), 3.95 (d, J = 3.2 Hz, 2H), 3.13 (d, J =18.8 Hz, 3H), 2.41 (s, 3H), 1.35 (dd, J = 14.7, 6.4 Hz, 3H) F21 147-152ESIMS 677 (400 MHz, CDCl₃) δ ¹⁹F NMR (376 MHz, CDCl₃) ([M + H]⁺) 8.52(s, 1H), 7.71 (d, J = 8.7 Hz, δ −58.03, −116.62, −116.80 2H), 7.51 (d, J= 7.9 Hz, 1H), 7.38 (d, J = 8.8 Hz, 3H), 6.93 (s, 1H), 6.68 (d, J = 10.3Hz, 2H), 6.50 (s, 1H), 5.19 (s, 2H), 4.15 (dt, J = 12.8, 6.4 Hz, 1H),4.03-3.87 (m, 2H), 3.15 (d, J = 31.9 Hz, 3H), 2.41 (s, 3H), 1.36 (dd, J= 25.5, 6.4 Hz, 3H) F22 165-167 ESIMS 627 (400 MHz, CDCl₃) δ ¹⁹F NMR(376 MHz, CDCl₃) ([M + H]⁺) 8.52 (s, 1H), 7.71 (dd, J = 2.4, δ −58.076.8 Hz, 2H), 7.46-7.29 (m, 5H), 7.29 (d, J = 5.0 Hz, 1H), 7.13 (s, 1H),7.07-6.99 (m, 3H), 5.20 (s, 2H), 4.37-4.25 (m, 2H), 3.91 (d, J = 2.2 Hz,2H), 3.27 (s, 3H), 2.42 (s, 3H) F23 139-141 ESIMS 643 (400 MHz, CDCl₃) δ¹⁹F NMR (376 MHz, CDCl₃) ([M + H]⁺) 8.52 (s, 1H), δ −58.07, −127.808.23-8.08 (m, 1H), 7.73-7.69 (m, 2H), 7.37 (d, J = 8.3 Hz, 2H), 7.28 (d,J = 8.8 Hz, 1H), 7.23 (s, 2H), 6.91 (s, 1H), 6.86-6.80 (m, 2H), 5.19 (s,2H), 3.95 (d, J = 2.4 Hz, 2H), 2.38-2.34 (m, 5H), 1.60-1.52 (m, 2H),0.91 (t, J = 7.3 Hz, 3H) F24 132-134 ESIMS 646 (400 MHz, CDCl₃) δ ¹⁹FNMR (376 MHz, CDCl₃) ([M + H]⁺) 8.52 (s, 1H), 8.16 (t, J = 6.0 Hz, δ−58.07, −127.94 1H), 7.71 (d, J = 7.8 Hz, 2H), 7.38 (dd, J = 2.2, 7.7Hz, 3H), 7.29 (d, J = 7.6 Hz, 1H), 7.20 (d, J = 1.2 Hz, 1H), 6.99 (s,1H), 6.85-6.79 (m, 2H), 5.19 (s, 2H), 4.38-4.25 (m, 2H), 3.95 (d, J =2.4 Hz, 2H), 3.26 (s, 3H), 2.42 (s, 3H) F25 140-142 ESIMS 639 (400 MHz,DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.32 (s, 1H), 8.95 (s, d₆)δ −56.99 1H), 7.99 (d, J = 9.2 Hz, 2H), 7.59 (d, J = 9.2 Hz, 2H), 7.38(d, J = 8.0 Hz, 1H), 7.25 (d, J = 8.0 Hz, 1H), 7.06 (t, J = 5.5 Hz, 2H),6.89 (d, J = 1.5 Hz, 1H), 6.83 (dd, J = 1.7 Hz, 1H), 5.15 (s, 2H), 4.13(d, J = 18.4 Hz, 1H), 4.02 (d, J = 18.4 Hz, 1H), 2.66 (td, J = 6.8, 13.7Hz, 1H), 2.30 (s, 3H), 2.08 (s, 3H), 1.18 (d, J = 6.8 Hz, 3H), 1.18 (d,J = 6.8 Hz, 3H) F26 115-117 ESIMS 639 (400 MHz, DMSO-d₆) δ ¹⁹F NMR (376MHz, DMSO- ([M + H]⁺) 9.32 (s, 1H), 8.96 (s, d₆) δ −56.99 1H), 7.99 (d,J = 9.6 Hz, 2H), 7.59 (d, J = 9.2 Hz, 2H), 7.28 (d, J = 7.8 Hz, 1H),7.20 (d, J = 8.8 Hz, 1H), 7.08 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 2.4 Hz,1H), 6.83 (dd, J = 2.4, 8.8 Hz, 1H), 5.15 (s, 2H), 4.14 (d, J = 18.4 Hz,1H), 4.04 (d, J = 18.4 Hz, 1H), 2.39-2.24 (m, 5H), 2.09 (s, 3H),1.62-1.36 (m, 2H), 0.86 (t, J = 7.6 Hz, 3H) F27 160-163 ESIMS 641 (400MHz, DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.32 (s, 1H), 8.96(s, d₆) δ −56.99 1H), 7.99 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 8.3 Hz,2H), 7.41 (d, J = 7.8 Hz, 1H), 7.28 (d, J = 5.0 Hz, 1H), 7.14 (s, 1H),7.09 (d, J = 5.5 Hz, 1H), 6.89 (d, J = 2.0 Hz, 1H), 6.83 (dd, J = 1.5,5.0 Hz, 1H), 5.15 (s, 2H), 4.28 (s, 2H), 4.08-3.93 (m, 2H), 3.21 (s,3H), 2.35 (s, 3H), 2.09 (s, 3H) F28 169-172 ESIMS 662 (300 MHz, DMSO-d₆)δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.34 (s, 1H), 9.15 (s, d₆) δ−56.95, −117.11 1H), 7.99 (d, J = 9.6 Hz, 2H), 7.59 (d, J = 10.0 Hz,2H), 7.28 (d, J = 8.6 Hz, 1H), 7.21 (d, J = 9.3 Hz, 1H), 7.09 (s, 1H),6.92 (d, J = 10.6 Hz, 2H), 5.25 (s, 2H), 4.21-4.00 (m, 2H), 2.35-2.31(m, 5H), 1.54-1.47 (m, 2H), 0.86 (t, J = 7.3 Hz, 3H) F29 147-149 ESIMS659 (300 MHz, DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.34 (s,1H), 9.09 (s, d₆) δ −56.99 1H), 7.99 (d, J = 5.5 Hz, 2H), 7.60 (d, J =8.8 Hz, 2H), 7.40-7.30 (m, 2H), 7.30-7.20 (m, 2H), 5.25 (s, 2H),4.24-3.85 (m, 2H), 2.68-2.63 (m, 1H), 2.30 (s, 3H), 1.73-1.36 (m, 3H),0.86 (t, J = 7.3 Hz, 3H) F30 145-147 ESIMS 659 (400 MHz, DMSO-d₆) δ ¹⁹FNMR (376 MHz, DMSO- ([M + H]⁺) 9.33 (s, 1H), 9.02 (s, d₆) δ −56.99 1H),7.99 (d, J = 9.3 Hz, 2H), 7.59 (d, J = 8.8 Hz, 2H), 7.37-7.25 (m, 4H),7.08 (s, 1H), 7.01 (d, J = 4.0 Hz, 1H), 5.23 (s, 2H), 4.17 (d, J = 18.1Hz, 1H), 4.04 (d, J = 11.2 Hz, 1H), 2.39-2.22 (m, 5H), 1.59-1.36 (m,2H), 0.86 (t, J = 7.3 Hz, 3H) F31 148-150 ESIMS 661 (300 MHz, DMSO-d₆) δ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.34 (s, 1H), 9.04 (s, d₆) δ −56.961H), 8.00 (d, J = 8.8 Hz, 2H), 7.59 (d, J = 8.8 Hz, 2H), 7.46-7.26 (m,3H), 7.22 (br s, 1H), 7.14 (s, 1H), 7.02 (d, J = 10.0 Hz, 1H), 5.23 (s,2H), 4.28 (s, 2H), 4.21-3.91 (m, 2H), 3.21 (s, 3H), 2.35 (s, 3H) F32159-161 ESIMS 655 (300 MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M +H]⁺) 9.33 (s, 1H), d₆) δ −56.96 8.13-7.89 (m, 3H), 7.59 (d, J = 8.8 Hz,3H), 7.38 (d, J = 8.0 Hz, 1H), 7.26 (d, J = 9.0 Hz, 1H), 7.03 (s, 1H),6.74 (s, 1H), 6.63 (br d, J = 9.6 Hz, 1H), 5.18 (s, 2H), 4.18 (d, J =20.0 Hz, 1H), 4.04 (d, J = 20.0 Hz, 1H), 3.74 (s, 3H), 2.82-2.55 (m,1H), 2.31 (s, 3H), 1.16-1.68 (m, 6H) F33 148-150 ESIMS 655 (300 MHz,DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.33 (s, 1H), 8.06 (s, d₆)δ −56.96 1H), 7.99 (d, J = 10.0 Hz, 2H), 7.59 (d, J = 9.66 Hz, 3H),7.38-7.20 (m, 2H), 7.06 (s, 1H), 6.74 (d, J = 2.2 Hz, 1H), 6.69-6.44 (m,1H), 5.18 (s, 2H), 4.27-3.95 (m, 2H), 3.75 (s, 3H), 2.38-2.20 (m, 5H),1.58-1.35 (m, 2H), 0.85 (t, J = 7.3 Hz, 3H) F34 158-161 ESIMS 657 (300MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.33 (s, 1H), 8.12(s, d₆) δ −56.96 1H), 7.99 (d, J = 10.3 Hz, 2H), 7.65-7.54 (m, 3H), 7.41(d, J = 7.7 Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H), 7.12 (s, 1H), 6.74 (d, J= 2.3 Hz, 1H), 6.63 (d, J = 10.0 Hz, 1H), 5.18 (s, 2H), 4.25 (s, 2H),4.20-3.93 (m, 2H), 3.74 (s, 3H), 3.20 (s, 3H), 2.35 (s, 3H) F35 190-192ESIMS 643 (400 MHz, DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.77(s, 1H), 9.33 (s, d₆) δ −57.00, −132.86 1H), 7.98 (d, J = 5.5 Hz, 2H),7.62-7.54 (m, 3H), 7.36 (t, J = 5.0 Hz, 2H), 7.28-7.20 (m, 2H), 7.04 (s,1H), 5.21 (s, 2H), 4.19 (d, J = 18.2 Hz, 1H), 4.05 (d, J = 18.2 Hz, 1H),2.69-2.60 (m, 1H), 2.30 (s, 3H), 1.16-1.70 (m, 6H) F36 149-151 ESIMS 643(400 MHz, DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.75 (s, 1H),9.33 (s, d₆) δ −57.00, −132.86 1H), 7.98 (d, J = 9.3 Hz, 2H), 7.64-7.53(m, 3H), 7.37-7.18 (m, 4H), 7.07 (s, 1H), 5.21 (s, 2H), 4.19 (d, J =18.1 Hz, 1H), 4.05 (d, J = 18.1 Hz, 1H), 2.37-2.24 (m, 5H), 1.62-1.40(m, 2H), 0.85 (t, J = 7.3 Hz, 3H) F37 199-201 ESIMS 645 (400 MHz,DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.74 (s, 1H), 9.33 (s, d₆)δ −57.00, −132.85 1H), 7.98 (d, J = 9.3 Hz, 2H), 7.68-7.49 (m, 3H), 7.41(d, J = 7.8 Hz, 1H), 7.37-7.21 (m, 3H), 7.13 (s, 1H), 5.21 (s, 2H), 4.25(s, 2H), 4.18-3.99 (m, 2H), 3.19 (s, 3H), 2.34 (s, 3H) F38 202-204 ESIMS659 (400 MHz, DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.76 (s,1H), 9.33 (s, d₆) δ −57.00 1H), 7.98 (d, J = 5.5 Hz, 2H), 7.80 (d, J =2.4 Hz, 1H), 7.59 (d, J = 8.3 Hz, 2H), 7.50 (dd, J = 1.5, 5.5 Hz, 1H),7.38 (d, J = 7.8 Hz, 1H), 7.25 (d, J = 5.5 Hz, 2H), 7.04 (s, 1H), 5.23(s, 2H), 4.19 (d, J = 18.4 Hz, 1H), 4.05 (d, J = 18.2 Hz, 1H), 2.64 (td,J = 6.8, 13.3 Hz, 1H), 2.30 (s, 3H), 1.21-1.01 (m, 6H) F39 158-160 ESIMS659 (400 MHz, DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.75 (s,1H), 9.33 (s, d₆) δ −57.00 1H), 7.99 (d, J = 5.5 Hz, 2H), 7.80 (d, J =2.4 Hz, 1H), 7.59 (d, J = 8.8 Hz, 2H), 7.50 (dd, J = 2.4, 9.3 Hz, 1H),7.33-7.17 (m, 3H), 7.06 (s, 1H), 5.24 (s, 2H), 4.20 (d, J = 18.1 Hz,1H), 4.05 (d, J = 18.2 Hz, 1H), 2.38-2.24 (m, 5H), 1.49 (qd, J = 7.4,15.0 Hz, 2H), 0.85 (t, J = 7.3 Hz, 3H) F40 186-188 ESIMS 661 (400 MHz,DMSO-d₆) δ ¹⁹F NMR (376 MHz, DMSO- ([M + H]⁺) 9.74 (s, 1H), 9.33 (s, d₆)δ −57.00 1H), 7.99 (d, J = 8.8 Hz, 2H), 7.79 (d, J = 2.4 Hz, 1H), 7.59(d, J = 8.3 Hz, 2H), 7.49 (dd, J = 2.4, 8.8 Hz, 1H), 7.41 (d, J = 7.4Hz, 1H), 7.27 (t, J = 9.0 Hz, 2H), 7.13 (s, 1H), 5.24 (s, 2H), 4.25 (s,2H), 4.18-4.00 (m, 2H), 3.19 (s, 3H), 2.34 (s, 3H) F41 239-242 ESIMS 662(300 MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.96 (s, 1H),9.31 (s, d₆) δ −56.96, −127.10 1H), 7.96 (d, J = 8.8 Hz, 2H), 7.58 (d, J= 8.4 Hz, 2H), 7.47-7.32 (m, 3H), 7.25 (d, J = 7.6 Hz, 1H), 7.04 (s,1H), 5.13 (s, 2H), 4.22 (d, J = 18.0 Hz, 1H), 4.075 (d, J = 18.0 Hz,1H), 2.63 (td, J = 6.6, 13.5 Hz, 1H), 2.30 (s, 3H), 1.10 (dd, J = 7.0,15.8 Hz, 6H) F42 185-187 ESIMS 662 (300 MHz, DMSO-d₆) δ ¹⁹F NMR (282MHz, DMSO- ([M + H]⁺) 9.95 (s, 1H), 9.31 (s, d₆) δ −56.96, −127.11 1H),7.96 (d, J = 9.2 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 12.0Hz, 2H), 7.28 (d, J = 8.6 Hz, 1H), 7.21 (d, J = 8.6 Hz, 1H), 7.06 (s,1H), 5.14 (s, 2H), 4.23 (d, J = 18.0 Hz, 1H), 4.06 (d, J = 18.0 Hz, 1H),2.28-2.19 (m, 5H), 1.48-1.40 (m, 2H), 0.84 (t, J = 7.3 Hz, 3H) F43208-210 ESIMS 664 (300 MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M +H]⁺) 9.94 (s, 1H), 9.31 (s, d₆) δ −56.97 1H), 7.96 (dd, J = 2.6, 7.6 Hz,2H), 7.58 (d, J = 8.4 Hz, 2H), 7.46-7.33 (m, 3H), 7.28 (d, J = 9.0 Hz,1H), 7.14 (s, 1H), 5.14 (s, 2H), 4.24 (s, 2H), 4.35-4.00 (m, 2H), 3.18(s, 3H), 2.34 (s, 3H) F44 156-158 ESIMS 626 (300 MHz, DMSO-d₆) δ ¹⁹F NMR(282 MHz, DMSO- ([M + H]⁺) 9.55 (s, 1H), 9.25 (s, d₆) δ −57.00 1H), 8.27(d, J = 1.7 Hz, 1H), 7.94 (dd, J = 1.2, 4.5 Hz, 2H), 7.58-7.51 (m, 3H),7.37 (d, J = 5.2 Hz, 1H), 7.25 (d, J = 4.2 Hz, 1H), 7.02 (s, 1H), 6.38(d, J = 6.2 Hz, 1H), 5.24 (d, J = 2.2 Hz, 2H), 4.20-4.03 (m, 2H),2.66-2.61 (m, 1H), 2.29 (s, 3H), 1.14-1.06 (m, 6H) F45 166-168 ESIMS 627(300 MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.58 (s, 1H),9.23 (s, d₆) δ −56.97 1H), 8.27 (d, J = 3.0 Hz, 1H), 7.96-7.91 (m, 2H),7.59-7.50 (m, 3H), 7.27 (d, J = 9.0 Hz, 1H), 7.20 (d, J = 9.0 Hz, 1H),7.056 (br s, 1H), 5.24 (s, 2H), 4.22-4.01 (m, 2H), 2.32-2.37 (m, 5H),1.51-1.43 (m, 2H), 0.84 (t, J = 7.6 Hz, 3H) F46 148-151 ESIMS 629 (300MHz, DMSO-d₆) δ ¹⁹F NMR (282 MHz, DMSO- ([M + H]⁺) 9.58 (s, 1H), 9.23(s, d₆) δ −56.97 1H), 8.26 (d, J = 3.0 Hz, 1H), 7.94 (dd, J = 2.3, 7.6Hz, 2H), 7.57 (d, J = 9.3 Hz, 2H), 7.51 (dd, J = 2.6, 10.3 Hz, 1H), 7.40(d, J = 9.0 Hz, 1H), 7.27 (d, J = 8.6 Hz, 1H), 7.12 (s, 1H), 6.38 (d, J= 11.0 Hz, 1H), 5.24 (s, 2H), 4.24 (s, 2H), 4.15-4.00 (m, 2H), 3.19 (s,3H), 2.34 (d, J = 5.0 Hz, 3H)

BAW & CL Rating Table % Control (or Mortality) Rating 50-100 A More than0-Less than 50 B Not Tested C No activity noticed in this bioassay D

YFM Rating Table % Control (or Mortality) Rating 80-100 A More than0-Less than 80 B Not Tested C No activity noticed in this bioassay D

TABLE ABC Biological Results Species No. BAW CL YFM F1 A A C F2 A A C F3A A C F4 A A C F5 A A A F6 A A C F7 A A C F8 A A A F9 A A A F10 D D CF11 D D C F12 A A C F13 A A C F14 A A C F15 A A C F16 A A C F17 A A AF18 A A C F19 A A C F20 A A C F21 C C C F22 C C C F23 A A C F24 C C CF25 A A C F26 A A C F27 A A C F28 C C C F29 A A C F30 A A C F31 C C CF32 A A C F33 A A C F34 A A C F35 A A C F36 A A C F37 A A C F38 A A CF39 A A C F40 A A C F41 A A A F42 A A C F43 A A C F44 A A C F45 B D CF46 B D C

1. A molecule having the following formula

wherein: (A) Ar¹ is selected from the group consisting of furanyl,phenyl, pyridazinyl, pyridyl, pyrimidinyl, or thienyl, wherein eachfuranyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, and thienyl may beoptionally substituted with one or more substituents independentlyselected from the group consisting of H, F, Cl, Br, I, CN, NO₂,(C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,(C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y), (C₁-C₄)alkyl-NR^(x)R^(y),C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy, wherein eachalkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl,phenyl, and phenoxy substituent may be optionally substituted with oneor more substituents independently selected from the group consisting ofH, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy; (B) Het is a5- or 6-membered, saturated or unsaturated, heterocyclic ring,containing one or more heteroatoms independently selected from nitrogen,sulfur, or oxygen, and where Ar¹ and 0 are not ortho to each other, butmay be meta or para, such as, for a five-membered ring they are 1,3, andfor a 6-membered ring they are either 1,3 or 1,4, wherein eachheterocyclic ring may be optionally substituted with one or moresubstituents independently selected from the group consisting of H, F,Cl, Br, I, CN, NO₂, oxo, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, S(O)_(n)—, —(C₁-C₄)alkyl, S(O)_(n)—, —(C₁-C₄)haloalkyl,OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy, wherein eachalkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl,phenyl, and phenoxy substituent may be optionally substituted with oneor more substituents independently selected from the group consisting ofH, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—, —(C₁-C₄)haloalkyl,OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy; (C) L¹ isselected from the group consisting of O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-O, O—(C₁-C₄)haloalkyl,(C₁-C₄)haloalkyl-O, O—(C₃-C₈)cycloalkyl, (C₃-C₈)cycloalkyl-O,O—(C₁-C₄)haloalkoxy, (C₁-C₄)haloalkoxy-O, O—(C₂-C₆)alkenyl,(C₂-C₆)alkenyl-O, O—(C₂-C₆)alkynyl, and O—(C₂-C₆)alkynyl, wherein eachalkyl, haloalkyl, cycloalkyl, alkenyl, and alkynyl may be optionallysubstituted with one or more substituents independently selected fromthe group consisting of H, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl,(C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy,(C₂-C₆)alkenyl, and (C₂-C₆)alkynyl; (D) Ar² is selected from the groupconsisting of furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl, orthienyl, wherein each furanyl, phenyl, pyridazinyl, pyridyl,pyrimidinyl, and thienyl may be optionally substituted with one or moresubstituents independently selected from the group consisting of H, F,Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y), (C₁-C₄)alkyl-NR^(x)R^(y),C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy, wherein eachalkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl,phenyl, and phenoxy substituent may be optionally substituted with oneor more substituents independently selected from the group consisting ofH, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy; (E) R¹⁵ isselected from the group consisting of H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, C(O)—NR^(x)R^(y), C(O)-phenyl,(C₁-C₄)alkyl-NR^(x)R^(y), C(O)O—(C₁-C₄)alkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,wherein each alkyl, cycloalkyl, alkenyl, alkynyl, and phenyl may beoptionally substituted with one or more substituents independentlyselected from the group consisting of H, F, Cl, Br, I, CN, NO₂, oxo,(C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,(C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y), (C₁-C₄)alkyl-NR^(x)R^(y),C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy; (F) Q¹ isselected from the group consisting of O and S; (G) Q² is selected fromthe group consisting of O and S; (H) R¹⁶ is selected from the groupconsisting of (K), H, (C₁-C₄)alkyl, (C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, C(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl, (C₁-C₄)alkylphenyl,(C₁-C₄)alkyl-O-phenyl, C(O)-(Het-1), (Het-1), (C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-C(O)-(Het-1),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(NR^(x)R^(y))—C(O)OH,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(N(R^(x))—C(O)O—(C₁-C₄)alkyl)-C(O)OH,(C₁-C₄)alkyl-C(O)-(Het-1)-C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₃-C₈)cycloalkyl, (C₁-C₄)alkyl-OC(O)-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-NR^(x)R^(y), (C₁-C₄)alkyl-S(O)_(n)-(Het-1), and(C₁-C₄)alkyl-O-(Het-1), wherein each alkyl, cycloalkyl, alkenyl,alkynyl, phenyl, and (Het-1) may be optionally substituted with one ormore substituents independently selected from the group consisting of H,F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)OH, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl), phenyl, phenoxy,Si((C₁-C₄)alkyl)₃, S(O)_(n)—NR^(x)R^(y), and (Het-1); (I) R¹⁷ isselected from the group consisting of (K), H, (C₁-C₄)alkyl,(C₃-C₈)cycloalkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, C(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,(C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl, C(O)-(Het-1), (Het-1),(C₁-C₄)alkyl-(Het-1), (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-(Het-1),(C₁-C₄)alkyl-C(O)-(Het-1),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(NR^(x)R^(y))—C(O)OH,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-NR^(x)R^(y),(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-C(O)—N(R^(x))(C₁-C₄)alkyl(N(R^(x))—C(O)O—(C₁-C₄)alkyl)-C(O)OH,(C₁-C₄)alkyl-C(O)-(Het-1)-C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl,(C₁-C₄)alkyl-OC(O)—(C₃-C₈)cycloalkyl, (C₁-C₄)alkyl-OC(O)-(Het-1),(C₁-C₄)alkyl-OC(O)—(C₁-C₄)alkyl-N(R^(x))—C(O)O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-NR^(x)R^(y), (C₁-C₄)alkyl-S(O)_(n)-(Het-1), and(C₁-C₄)alkyl-O-(Het-1), wherein each alkyl, cycloalkyl, alkenyl,alkynyl, phenyl, and (Het-1) may be optionally substituted with one ormore substituents independently selected from the group consisting of H,F, Cl, Br, I, CN, NO₂, NR^(x)R^(y), (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)OH, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy,Si((C₁-C₄)alkyl)₃, S(O)_(n)—NR^(x)R^(y), and (Het-1); (J) L² is selectedfrom the group consisting of (C₃-C₈)cycloalkyl, phenyl,(C₁-C₄)alkylphenyl, (C₁-C₄)alkyl-O-phenyl, (C₂-C₆)alkenyl-O-phenyl,(Het-1), (C₁-C₄)alkyl-(Het-1), and (C₁-C₄)alkyl-O-(Het-1), wherein eachalkyl, cycloalkyl, alkenyl, phenyl, and (Het-1) may be optionallysubstituted with one or more substituents independently selected fromthe group consisting of H, F, Cl, Br, I, CN, NO₂, NR^(x)R^(y),(C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,(C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₁-C₄)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,O—(C₁-C₄)alkyl, S—(C₁-C₄)alkyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy, and (Het-1),wherein each alkyl, cycloalkyl, alkenyl, phenyl, and (Het-1) substituentmay be optionally substituted with one or more substituentsindependently selected from the group consisting of H, F, Cl, Br, I, CN,NO₂, NR^(x)R^(y), (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₁-C₄)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,O—(C₁-C₄)alkyl, S—(C₁-C₄)alkyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, phenoxy, and (Het-1); (K)R¹⁶ and R¹² along with C^(x)(Q²)(N^(x)), form a 4- to 7-memberedsaturated or unsaturated, heterocyclic ring, which may further containone or more heteroatoms selected from the group consisting of nitrogen,sulfur, and oxygen, wherein each heterocyclic ring may be optionallysubstituted with one or more substituents independently selected fromthe group consisting of oxo, R¹⁸, and R¹⁹, wherein R¹⁸ and R¹⁹ are eachindependently selected from the group consisting of H, F, Cl, Br, I, CN,NO₂, oxo, thioxo, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and (Het-1); (L) R^(x) andR^(y) are each independently selected from the group consisting of H,(C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,(C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, and phenyl, wherein each alkyl,haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl, and phenylmay be optionally substituted with one or more substituentsindependently selected from the group consisting of H, F, Cl, Br, I, CN,NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy,(C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)H, C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and (Het-1); (M) (Het-1)is a 5- or 6-membered, saturated or unsaturated, heterocyclic ring,containing one or more heteroatoms independently selected from the groupconsisting of nitrogen, sulfur, or oxygen, wherein each heterocyclicring may be optionally substituted with one or more substituentsindependently selected from the group consisting of H, F, Cl, Br, I, CN,NO₂, oxo, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₃-C₈)cycloalkyl,(C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl,S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl, OSO₂—(C₁-C₄)alkyl,OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y), (C₁-C₄)alkyl-NR^(x)R^(y),C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl, C(O)—(C₁-C₄)haloalkyl,C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl, C(O)O—(C₃-C₈)cycloalkyl,C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl, (C₁-C₄)alkyl-O—(C₁-C₄)alkyl,(C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy, wherein eachalkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkenyl, alkynyl,phenyl, and phenoxy substituent may be optionally substituted with oneor more substituents independently selected from the group consisting ofH, F, Cl, Br, I, CN, NO₂, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl,(C₃-C₈)cycloalkyl, (C₁-C₄)alkoxy, (C₁-C₄)haloalkoxy, (C₂-C₆)alkenyl,(C₂-C₆)alkynyl, S(O)_(n)—(C₁-C₄)alkyl, S(O)_(n)—(C₁-C₄)haloalkyl,OSO₂—(C₁-C₄)alkyl, OSO₂—(C₁-C₄)haloalkyl, C(O)—NR^(x)R^(y),(C₁-C₄)alkyl-NR^(x)R^(y), C(O)—(C₁-C₄)alkyl, C(O)O—(C₁-C₄)alkyl,C(O)—(C₁-C₄)haloalkyl, C(O)O—(C₁-C₄)haloalkyl, C(O)—(C₃-C₈)cycloalkyl,C(O)O—(C₃-C₈)cycloalkyl, C(O)—(C₂-C₆)alkenyl, C(O)O—(C₂-C₆)alkenyl,(C₁-C₄)alkyl-O—(C₁-C₄)alkyl, (C₁-C₄)alkyl-S(O)_(n)—(C₁-C₄)alkyl,C(O)—(C₁-C₄)alkyl-C(O)O—(C₁-C₄)alkyl, phenyl, and phenoxy; (N) n areeach independently 0, 1, or 2; and N-oxides, agriculturally acceptableacid addition salts, salt derivatives, solvates, crystal polymorphs,isotopes, resolved stereoisomers, and tautomers, of the molecules ofFormula One.
 2. A molecule according to claim 1, wherein Ar¹ is (1a)

wherein: (1) R¹, R², R⁴, and R⁵ are each independently H; and (2) R³ isOCF₃.
 3. A molecule according to claim 1, wherein Het is (1b)

wherein R⁶ is H.
 4. A molecule according to claim 1, wherein 0 is (1c)

wherein R⁷ and R⁹ are each independently H.
 5. A molecule according toclaim 1, wherein 0 is (1d)

wherein R⁸ and R¹⁰ are each independently H.
 6. A molecule according toclaim 1, wherein Ar² is (1e)

wherein: (1) R¹¹ and R¹² are each independently H or F; (2) X¹ is N orCR¹³, wherein R¹³ is H, F, Cl, CH₃ or OCH₃; and (3) X² is N or CR¹⁴,wherein R¹⁴ is H, F, Cl, or OCH₃.
 7. A molecule according to claim 1,wherein R¹⁵ is H.
 8. A molecule according to claim 1, wherein Q¹ is O.9. A molecule according to claim 1, wherein Q² is S.
 10. A moleculeaccording to claim 1, wherein L² is (1f)

wherein: (1) R²⁰ is CH₂CH₂CH₃, CH(CH₃)₂, CH₂OCH₃, or CH(CH₃)OCH₃; (2)R²¹ is H; (3) R²² is H or F; (4) R²³ is CH₃; and (5) R²⁴ is H.
 11. Amolecule according to claim 1, wherein R¹⁶ and R¹⁷ along withC^(x)(Q²)(N^(x)), is (1g)

wherein R¹⁸ and R¹⁹ are each independently H.
 12. A molecule accordingto claim 1, wherein (A) Ar¹ is (1a)

wherein, R¹, R², R³, R⁴, and R⁵ are each independently selected from thegroup consisting of H and (C₁-C₄)haloalkoxy; (B) Het is (1b)

wherein, R⁶ is H; (C) L¹ is selected from the group consisting of

wherein, R⁷, R⁸, R⁹, and R¹⁹ are each independently H; (D) Ar² is (1e)

wherein: (1) X¹ is selected from the group consisting of N and CR¹³, (2)X² is selected from the group consisting of N and CR¹⁴, and (3) R¹¹,R¹², R¹³, and R¹⁴ are each independently selected from the groupconsisting of H, F, Cl, (C₁-C₄)alkyl, and (C₁-C₄)alkoxy; (E) R¹⁵ is H;(F) Q¹ is O; (G) Q² is S; (H) R¹⁶ is (K); (I) R¹⁷ is (K); (J) L² is (1f)

wherein, R²⁰, R²¹, R²², R²³, and R²⁴ are each independently selectedfrom the group consisting of H, F, (C₁-C₄)alkyl, and(C₁-C₄)alkyl-O—(C₁-C₄)alkyl; and (K) R¹⁶ and R¹⁷ along withC^(x)(Q²)(N^(x)), is (1g)

wherein, R¹⁸ and R¹⁹ are each independently H.
 13. A molecule accordingto claim 1, wherein (A) Ar¹ is (1a)

wherein, R¹, R², R³, R⁴, and R⁵ are each independently selected from thegroup consisting of H and OCF₃; (B) Het is (1b)

wherein, R⁶ is H; (C) L¹ is selected from the group consisting of

wherein, R⁷, R⁸, R⁹, and R¹⁰ are each independently H; (D) Ar² is (1e)

wherein: (1) X¹ is selected from the group consisting of N and CR¹³, (2)X² is selected from the group consisting of N and CR¹⁴, and (3) R¹¹,R¹², R¹³, and R¹⁴ are each independently selected from the groupconsisting of H, F, Cl, CH₃, and OCH₃; (E) R¹⁵ is H; (F) Q¹ is O; (G) Q²is S; (H) R¹⁶ is (K); (I) R¹⁷ is (K); (J) L² is (1f)

wherein, R²⁰, R²¹, R²², R²³, and R²⁴ are each independently selectedfrom the group consisting of H, F, CH₃, CH₂CH₂CH₃, CH(CH₃)₂, CH₂OCH₃,and CH(CH₃)OCH₃; and (K) R¹⁶ and R¹⁷ along with C^(x)(Q²)(N^(x)), is(1g)

wherein, R¹⁸ and R¹⁹ are each independently H.
 14. A molecule accordingto claim 1 wherein said molecule is selected from one of the followingmolecules No. Structure F1

F2

F3

F4

F5

F6

F7

F8

F9

F12

F13

F14

F15

F16

F17

F18

F19

F20

F21

F22

F23

F24

F25

F26

F27

F28

F29

F30

F31

F32

F33

F34

F35

F36

F37

F38

F39

F40

F41

F42

F43

F44


15. A pesticidal composition comprising (a) a molecule according toclaim 1 and (b) an active ingredient.
 16. A process to control a pestsaid process comprising applying to a locus, a pesticidally effectiveamount of a molecule according to claim 1.